WO2021243971A1 - 一种复合纳米材料、制备方法及催化剂 - Google Patents

一种复合纳米材料、制备方法及催化剂 Download PDF

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WO2021243971A1
WO2021243971A1 PCT/CN2020/129538 CN2020129538W WO2021243971A1 WO 2021243971 A1 WO2021243971 A1 WO 2021243971A1 CN 2020129538 W CN2020129538 W CN 2020129538W WO 2021243971 A1 WO2021243971 A1 WO 2021243971A1
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dimensional
nanosheets
transition metal
preparation
platinum
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French (fr)
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王佳宏
杨娜
喻学锋
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深圳先进技术研究院
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group 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
    • 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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J27/045—Platinum group 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • This application relates to the technical field of nanomaterials, in particular to a composite nanomaterial, a preparation method and a catalyst.
  • the embodiments of the present application provide a composite nano material, a preparation method and a catalyst, which are used to solve the problems in the prior art.
  • This application provides a method for preparing a composite nano material, including:
  • the mixed liquid is reacted at a preset reaction temperature under a protective gas atmosphere to prepare a composite nano material.
  • the two-dimensional nanosheets specifically include any one or more of the following: graphene nanosheets, two-dimensional molybdenum disulfide nanosheets, two-dimensional black phosphorus nanosheets, two-dimensional hexagonal boron nitride nanosheets, Two-dimensional graphite-like carbon nitride nanosheets, two-dimensional transition metal sulfide nanosheets, two-dimensional transition metal carbide nanosheets, two-dimensional transition metal carbonitride nanosheets, two-dimensional transition metal oxides Nanosheets, two-dimensional transition metal hydroxide nanosheets.
  • the particles of the two-dimensional material containing the layered structure are dispersed in a second organic solvent, and the two-dimensional nanosheets are generated by ultrasonic peeling.
  • the first organic solvent specifically includes: a reducing organic solvent; and,
  • the second organic solvent specifically includes any one of the following: dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and absolute ethanol.
  • the ultrasonic frequency is 15-60 kHz
  • the ultrasonic power is 300-1800 W
  • the ultrasonic duration is 20-720 min.
  • the organic platinum salt specifically includes: platinum acetylacetonate; and,
  • the other transition metal salts specifically include: Co, Ni, Fe, Cu, Mo or W hydrochloride, sulfate, nitrate or acetylacetonate.
  • the sum of the molar concentrations of the organic platinum salt and other transition metal salts is 1.0-100.0 mM; and,
  • the molar ratio of the organic platinum salt to other transition metal salts is 0.1:1 to 1:1.
  • the specified molar ratio specifically includes: the molar ratio of the two-dimensional nanosheet to the metal salt precursor is 1:0.1 ⁇ 1:5, wherein: the amount of the metal salt precursor is specifically an organic platinum salt The sum of the amount of other transition metal salt substances.
  • the application also provides a composite nano material, which is prepared by using the method provided in the embodiment of the application.
  • the present application also provides a catalyst for producing hydrogen by electrolyzing water, and the catalyst includes the composite nanomaterial prepared by the method provided in the present application.
  • the two-dimensional nanosheets are dispersed in a first organic solvent to prepare a dispersion, and organic platinum salts and other transition metal salts are dissolved in the first organic solvent to prepare a mixed salt Then, the mixed salt solution and the dispersion are mixed according to a specified molar ratio, and then the mixed solution is reacted at a preset reaction temperature under a protective gas atmosphere, thereby preparing a composite nanomaterial.
  • a first organic solvent to prepare a dispersion
  • organic platinum salts and other transition metal salts are dissolved in the first organic solvent to prepare a mixed salt
  • the mixed salt solution and the dispersion are mixed according to a specified molar ratio, and then the mixed solution is reacted at a preset reaction temperature under a protective gas atmosphere, thereby preparing a composite nanomaterial.
  • the sheet has a very large specific surface area, which is conducive to the diffusion of reactants, can expose more active sites, is conducive to the rapid transfer of interfacial charges, improves the catalytic performance of the hydrogen production reaction, and improves the efficiency of hydrogen production to reduce energy consumption.
  • the preparation method has simple process flow and good repeatability, and the obtained composite nanomaterial has a stable structure. Compared with the direct use of metallic platinum as a catalyst for hydrogen production, the content of platinum in the catalyst is greatly reduced, and the catalyst is greatly reduced. Cost of use.
  • FIG. 1 is a schematic diagram of a specific process of a method for preparing a composite nanomaterial provided by an embodiment of the application;
  • FIG. 2 is a schematic diagram of a transmission electron microscope of a black phosphorous/platinum copper alloy composite nano material prepared by the preparation method provided in an embodiment of the application;
  • FIG. 3 is a schematic diagram of a transmission electron microscope of a graphene/platinum copper alloy composite nano material prepared by the preparation method provided in the embodiment of the application;
  • FIG. 4 is a schematic diagram of a transmission electron microscope of a molybdenum disulfide/platinum-copper alloy composite nanomaterial prepared by the preparation method provided in an embodiment of the application;
  • FIG. 5 is a test diagram of the acidic hydrogen evolution reaction performance of composite nanomaterials prepared in an embodiment of the application.
  • the biggest problem with the current technology of electrolyzed hydrogen production is high energy consumption. Therefore, it is necessary to provide a high-efficiency catalyst that can be used to electrolyze water to produce hydrogen, so as to improve the efficiency of hydrogen production and reduce energy consumption. Based on this, the embodiments of the present application provide a method for preparing composite nanomaterials, which can prepare an efficient catalyst for electrolyzing water to produce hydrogen, thereby solving this problem.
  • Fig. 1 is a schematic diagram of the specific process of the preparation method of the composite nanomaterial, and the preparation method includes the following steps:
  • Step S11 The two-dimensional material containing the layered structure is stripped to prepare a two-dimensional nanosheet.
  • a two-dimensional material containing a layered structure usually includes multiple layers, and two-dimensional nanosheets can be prepared by peeling off each of the layers.
  • a two-dimensional material with a layered structure can usually be any of the following crystals: graphite, black phosphorus, hexagonal boron nitride (h-BN), graphite-like carbon nitride (gC 3 N 4 ) , Molybdenum disulfide, graphite phase carbon nitride transition metal sulfide (TMD), two-dimensional transition metal carbide, two-dimensional transition metal carbonitride (MXene), transition metal oxide, transition metal hydroxide.
  • the specific method of preparing two-dimensional nanosheets from a two-dimensional material containing a layered structure by exfoliation it can usually be as follows: Disperse the particles in a second organic solvent, and then peel them off ultrasonically to generate two-dimensional nanosheets.
  • the ultrasonic peeling process Among them, the ultrasound frequency can be 15 ⁇ 60kHz, the ultrasound power can be 300 ⁇ 1800W, and the ultrasound duration can be 20 ⁇ 720min.
  • ultrasonic vibration is performed at a frequency of 40kHz and a power of 1500W for 200min.
  • the second organic solvent specifically includes any one of the following: dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and absolute ethanol.
  • centrifugal cleaning is usually required, and the product after centrifugal cleaning is vacuum dried, so as to finally obtain two-dimensional nanosheets.
  • the centrifugal speed can be 4000 ⁇ 10000rpm
  • the centrifugation time can be 5-40min
  • the solvent used can be absolute ethanol, propanol, etc.
  • peeling or electrochemical peeling can be used to peel the two-dimensional nanosheets from the two-dimensional material containing the layered structure.
  • the specific peeling method is not limited here.
  • Step S12 Disperse the two-dimensional nanosheets in the first organic solvent to prepare a dispersion.
  • the specific method can be as follows: weigh a certain amount of two-dimensional nanosheets and put them in the first organic solvent, and then use electromagnetic stirring or ultrasonic vibration to disperse the two-dimensional nanosheets in the first organic solvent to prepare a dispersion.
  • the first organic solvent may generally be a reducing organic solvent, so as to better reduce metal ions in subsequent reactions.
  • the first organic solvent may specifically be N,N-dimethyl. Formamide.
  • Step S13 Dissolve the organic platinum salt and other transition metal salts in the first organic solvent to prepare a mixed salt solution.
  • the organic platinum salt can usually be dissolved in the first organic solvent, for example, it may be platinum acetylacetonate.
  • the cation is a cation of a transition metal other than Pt, such as Co, Ni, Fe, Cu, Mo, W or other transition metal cations.
  • the valence of the cation is not limited, for example, It is 2+, 3+ or 5+, etc.
  • the anion can be sulfate, nitrate, chloride, or other anions.
  • the other transition metal salt is a hydrochloride, sulfate or nitrate of Co, Ni, Fe, Cu, Mo or W.
  • the other transition metal salts may also be organic salts of other transition metals, such as acetylacetonate of other transition metals.
  • the sum of the molar concentrations of the organic platinum salt and other transition metal salts can be: 1.0 ⁇ 100.0mM (millimoles per liter, mmol/L), such as 1mM, 10mM, 17mM, 30mM, 100mM or other concentrations between 1.0mM and 100.0mM.
  • the molar concentration ratio between the two can be: 0.1:1 to 1:1.
  • Step S14 Mix the mixed salt solution and the dispersion liquid in a designated molar ratio.
  • the two can be mixed at a specified molar ratio to obtain a mixed liquid.
  • the mixed solution can be fully stirred by means of magnetic stirring, mechanical stirring, etc.
  • the specified molar ratio can be specifically that the molar ratio of the two-dimensional nanosheets to the metal salt precursor is 1:0.1 ⁇ 1:5, where: the amount of the metal salt precursor is specifically the organic platinum salt and other transition metal salt substances The sum of the amounts.
  • the molar ratio of the two-dimensional nanosheet to the metal salt precursor is 1:0.1, 1:0.3, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.7, 1:2 , 1:2.4, 1:2.8, 1:3, 1:3.5, 1:4, 1:4.4, 1:4.6, 1:4.9, 1:5 or other between 1:0.1 and 1:5 value.
  • the molar ratio of the two-dimensional nanosheet to the metal salt precursor when the molar ratio of the two-dimensional nanosheet to the metal salt precursor is small (for example, close to about 1:5), the ratio of the metal salt precursor is relatively high at this time, and the load on the two-dimensional nanosheet The amount is relatively large, but there will also be more metal salt precursors that are not loaded, which leads to the waste of some metal salt precursors; on the contrary, when the moles of the two-dimensional nanosheets and the metal salt precursor are relatively large (such as When it is close to 1:0.1), the ratio of metal salt precursors is relatively low at this time, but it may also result in a relatively small load on the two-dimensional nanosheet. Therefore, the molar ratio of the two-dimensional nanosheet to the metal salt precursor can be further 1:0.3 to 1:1.5.
  • Step S15 The mixed solution is reacted at a preset reaction temperature under a protective gas atmosphere to prepare a composite nanomaterial.
  • the protective gas may include argon, nitrogen, or helium.
  • a certain amount of protective gas can be introduced into the reactor in advance to exhaust the air in the reactor and prevent the oxygen in the air from interfering with the reaction.
  • 30 minutes of nitrogen can be introduced into the reactor in advance to form a nitrogen atmosphere in the reactor.
  • the preset reaction temperature it can specifically be 80-200°C.
  • it is 80°C, 90°C, 100°C, 140°C, 200°C, or other temperatures between 80°C and 200°C.
  • reaction time of the reaction may be 10 to 480 minutes, for example, 260 minutes.
  • the reaction product obtained by this reaction can be obtained by filtration or centrifugal separation first.
  • the obtained reaction product can also be dispersed in absolute ethanol by ultrasonic vibration, and then centrifuged and washed, and the ultrasonic vibration and centrifugal washing are repeated 2 to 3 times to clean the reaction product.
  • the ultrasonic frequency is 15 ⁇ 60kHz and the ultrasonic duration is 1 ⁇ 3min; the centrifugal speed during centrifugal washing is 6000 ⁇ 10000rpm/min and the centrifugal time is 5 ⁇ 15min.
  • the reaction product after the final centrifugal washing can be placed in a vacuum drying oven for drying, and the resulting composite nano material can be obtained after drying.
  • the two-dimensional nanosheets are dispersed in a first organic solvent to prepare a dispersion, and organic platinum salts and other transition metal salts are dissolved in the first organic solvent to prepare
  • the salt solution is mixed, and then the mixed salt solution and the dispersion are mixed according to a specified molar ratio, and then the mixed solution is reacted at a preset reaction temperature under a protective gas atmosphere, thereby preparing a composite nanomaterial.
  • a two-dimensional nanosheet/platinum-based alloy composite nanomaterial can be prepared as an efficient catalyst for hydrogen production, which is beneficial to promote the chemical adsorption and activation of reactants, improve the catalytic performance of the hydrogen production reaction, and thereby improve the efficiency of hydrogen production To reduce energy consumption.
  • the preparation method provided in this application mainly uses hydrothermal method to grow platinum-based alloy nanoparticles on two-dimensional nanosheets. Compared with directly using metallic platinum as a catalyst for hydrogen production, it also greatly reduces the content of platinum in the catalyst. The cost is reduced; on the other hand, the preparation method has simple process flow and good repeatability, and the obtained composite nano material has a stable structure, which is beneficial to promote chemical adsorption and activation of reactants and improve catalytic performance.
  • two-dimensional nanosheets are used as the catalyst carrier, and platinum-based alloys are used as active sites. Because the two-dimensional nanosheets as the carrier have a very large specific surface area, it is conducive to the diffusion of reactants. Exposing more active sites is conducive to the rapid transfer of interfacial charges and improves the catalytic performance of the hydrogen production reaction.
  • the composite nanomaterial prepared by the preparation method provided in this application can be directly used as a catalyst for hydrogen production by electrolyzing water, thereby improving the efficiency of hydrogen production, and other additives can also be added to the composite nanomaterial.
  • the catalyst, or adding the composite nano material to other catalysts to improve the catalytic performance, are all within the protection scope of the present application.
  • step S11 and step S12 are mainly used to prepare a dispersion of two-dimensional nanosheets, and step S13 is used to prepare a mixed salt solution. Therefore, the order of execution of these two processes can be omitted.
  • a two-dimensional nanosheet dispersion can be prepared through steps S11 and S12 first, and then a mixed salt solution can be prepared through step S13, or a mixed salt solution can be prepared through step S13, and then step S11 and step S12 To prepare a dispersion of two-dimensional nanosheets, it can also be prepared simultaneously.
  • Black phosphorus is used as a two-dimensional material containing a layered structure to prepare two-dimensional nanosheets.
  • the organic platinum salt is platinum acetylacetonate; the other transition metal salts are copper acetylacetonate.
  • Fig. 2 is a schematic diagram of a transmission electron microscope of the two-dimensional black phosphorous nanosheet/platinum copper alloy composite nanomaterial, in which the layered structure is a two-dimensional black phosphorous nanosheet, and the black particles are a platinum copper alloy.
  • a small amount of phosphorus-oxygen bonds on the surface of the two-dimensional black phosphorus nanosheets and heated N,N-dimethylformamide are used to reduce the metal salt precursors to metal elements.
  • the presence of the platinum-based alloy composite structure is conducive to the diffusion of hydrogen production reactants and the exposure of active sites, and there is a synergistic catalytic effect between the components, which is conducive to the improvement of the catalytic performance during the hydrogen production reaction.
  • Graphene is used as a two-dimensional material with a layered structure to prepare two-dimensional nanosheets (called graphene nanosheets).
  • the organic platinum salt is platinum acetylacetonate; the other transition metal salts are copper acetylacetonate.
  • Fig. 3 is a schematic diagram of a transmission electron microscope of the graphene nanosheet/platinum-copper alloy composite nanomaterial, in which the sheet-like structure is graphene nanosheets, and the black particles are platinum-copper alloys.
  • Molybdenum disulfide is used as a two-dimensional material containing a layered structure to prepare two-dimensional nanosheets.
  • the organic platinum salt is platinum acetylacetonate; the other transition metal salts are copper acetylacetonate.
  • FIG. 4 is a schematic diagram of a transmission electron microscope of the two-dimensional molybdenum disulfide nanosheet/platinum-copper alloy composite nanomaterial, in which the laminar structure is a two-dimensional molybdenum disulfide nanosheet, and the black particles are a platinum-copper alloy.
  • Figure 5 shows the two-dimensional black phosphorous nanosheet/platinum copper alloy composite nanomaterial (BP-PtCu), graphene nanosheet/platinum copper alloy composite nanomaterial (G-PtCu) prepared in the above-mentioned examples 1 to 3 of this application. ), two-dimensional molybdenum disulfide nanosheet/platinum copper alloy composite nanomaterial (MoS 2 -PtCu), the acidic hydrogen evolution reaction performance test chart under the same test conditions, where the abscissa is the reversible hydrogen electrode (RHE) , The unit is V), the ordinate is the current density (Current Density, the unit is mA cm -2 ).
  • RHE reversible hydrogen electrode
  • the comparative example is a test chart of the acidic hydrogen evolution reaction performance under the same test conditions using pure graphite electrodes (C). It can be seen from the figure 5 that G-PtCu has the best performance, BP-PtCu is second, and MoS 2 -PtCu has the worst performance, but these three materials have better hydrogen evolution performance than pure graphite electrodes (C).
  • some two-dimensional nanosheets that meet both cost requirements and catalytic performance requirements can be selected as carriers, so as to prepare corresponding composite nanomaterials as electrolyzed water systems.
  • Hydrogen catalyst For example, considering the high cost of graphene nanosheets, but at the same time better catalytic performance, when a catalyst with high catalytic performance is required, graphene nanosheets can be selected as the carrier.
  • the graphene nanosheets can be prepared by ultrasonic peeling of graphite powder dispersed in N-methylpyrrolidone by using the method in the embodiments of the present application.
  • the ultrasonic frequency can be 15-60kHz
  • the ultrasonic power can be 300.
  • ⁇ 1800W and ultrasound duration can be 20 ⁇ 720min.

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Abstract

本申请公开了一种复合纳米材料、制备方法及催化剂。该方法包括：将二维纳米片分散于第一有机溶剂中以制备出分散液，并将有机铂盐和其他过渡金属盐溶解于所述第一有机溶剂以制备出混合盐溶液；按指定摩尔比将所述混合盐溶液与所述分散液进行混合；将混合液在保护气体氛围下，以预设反应温度进行反应，制得复合纳米材料。通过该制备方法，能够制备出二维纳米片/铂基合金复合纳米材料作为制氢的催化剂，有利于促进反应物的化学吸附与活化，因此能够提升制氢反应的催化性能，从而提高制氢效率以降低能耗。

Description

一种复合纳米材料、制备方法及催化剂 技术领域
本申请涉及纳米材料技术领域，尤其涉及一种复合纳米材料、制备方法及催化剂。
 背景技术
当前，化石能源的过度使用致使人们对环境和能源危机的焦虑日益加深，利用电解水方法制备清洁的氢能是实现可再生能源转化、进而解决能源与环境危机的一种有效策略。而电解水制氢技术目前最大的问题是高能耗。因此，提供能够用于电解水制氢的高效催化剂，从而提高制氢效率以降低能耗，是本申请所要解决的技术问题。
 技术问题
本申请实施例提供一种复合纳米材料、制备方法及催化剂，用于解决现有技术中的问题。
 技术解决方案
本申请提供一种复合纳米材料的制备方法，包括：
将二维纳米片分散于第一有机溶剂中以制备出分散液，并将有机铂盐和其他过渡金属盐溶解于所述第一有机溶剂以制备出混合盐溶液；
按指定摩尔比将所述混合盐溶液与所述分散液进行混合；
将混合液在保护气体氛围下，以预设反应温度进行反应，制得复合纳米材料。
优选的，所述二维纳米片，具体包括如下任意一种或多种：石墨烯纳米片、二维二硫化钼纳米片、二维黑磷纳米片、二维六方氮化硼的纳米片、二维类石墨相氮化碳的纳米片、二维过渡金属硫化物的纳米片、二维过渡金属碳化物的纳米片、二维过渡金属碳氮化物的纳米片、二维过渡金属氧化物的纳米片、二维过渡金属氢氧化物的纳米片。
优选的，将含层状结构的二维材料的颗粒分散于第二有机溶剂中，并通过超声剥离以生成所述二维纳米片。
优选的，所述第一有机溶剂具体包括：还原性的有机溶剂；以及，
所述第二有机溶剂具体包括如下任意一种：二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮、无水乙醇。
优选的，在通过超声剥离以生成所述二维纳米片过程中，超声频率为15~60kHz、超声功率为300~1800W以及超声时长为20~720min。
优选的，所述有机铂盐具体包括：乙酰丙酮铂；以及，
所述其他过渡金属盐具体包括：Co、Ni、Fe、Cu、Mo或W的盐酸盐、硫酸盐、硝酸盐或乙酰丙酮盐。
优选的，在所述混合盐溶液中，有机铂盐与其他过渡金属盐的摩尔浓度的总和为：1.0~100.0mM；以及，
在所述混合盐溶液中，有机铂盐与其他过渡金属盐的摩尔比为：0.1：1~1：1。
优选的，所述指定摩尔比具体包括：所述二维纳米片与金属盐前驱体的摩尔比为：1：0.1~1：5，其中：金属盐前驱体的物质的量具体为有机铂盐与其他过渡金属盐物质的量之和。
本申请还提供一种复合纳米材料，所述的复合纳米材料采用本申请实施例所提供的方法进行制备得到。
本申请还一种电解水制氢的催化剂，所述催化剂中包括本申请所提供的方法所制备出的复合纳米材料。
 有益效果
采用本申请所提供的制备方法，将二维纳米片分散于第一有机溶剂中以制备出分散液，并将有机铂盐和其他过渡金属盐溶解于所述第一有机溶剂以制备出混合盐溶液，然后按指定摩尔比将混合盐溶液与分散液进行混合，之后将混合液在保护气体氛围下，以预设反应温度进行反应，从而制得复合纳米材料。通过该制备方法，能够制备出二维纳米片/铂基合金复合纳米材料作为制氢的高效催化剂，其中以二维纳米片作为催化剂的载体，合金作为活性位点，由于作为载体的二维纳米片具有极大大的比表面积，有利于反应物的扩散，能够暴露出更多的活性位点，有利于界面电荷的快速转移，提升制氢反应使得催化性能，从而提高制氢效率以降低能耗。另外，该制备方法工艺流程简单、重复性好，所得到的复合纳米材料结构稳定，相对于直接以金属铂作为制氢时的催化剂，大大减少了铂元素在催化剂中的含量，大大降低了催化剂的使用成本。
 附图说明
此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1为本申请实施例提供的复合纳米材料的制备方法的具体流程示意图；
图2为本申请实施例提供的制备方法所制备出的，黑磷/铂铜合金复合纳米材料的透射电镜示意图；
图3为本申请实施例提供的制备方法所制备出的，石墨烯/铂铜合金复合纳米材料的透射电镜示意图；
图4为本申请实施例提供的制备方法所制备出的，二硫化钼/铂铜合金复合纳米材料的透射电镜示意图；
图5为本申请实施例所制备出的复合纳米材料的酸性析氢反应性能测试图。
 本发明的实施方式
为使本申请的目的、技术方案和优点更加清楚，下面将结合本申请具体实施例及相应的附图对本申请技术方案进行清楚、完整地描述。显然，所描述的实施例仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
以下结合附图，详细说明本申请各实施例提供的技术方案。
如前所示，目前电解水制氢技术最大的问题是高能耗。因此，需要提供能够用于电解水制氢的高效催化剂，从而提高制氢效率以降低能耗。基于此，本申请实施例提供一种复合纳米材料的制备方法，能够制备出电解水制氢的高效催化剂，从而解决该问题。
如图1所示为该复合纳米材料的制备方法的具体流程示意图，该制备方法包括如下步骤：
步骤S11：将含层状结构的二维材料通过剥离制备二维纳米片。
其中，含层状结构的二维材料中通常包括多个层，可以通过将其各层进行剥离而制备出二维纳米片。在实际应用中，含层状结构的二维材料通常可以是如下的任意一种晶体：石墨、黑磷、六方氮化硼（h-BN）、类石墨相氮化碳（g-C 3N 4）、二硫化钼、石墨相氮化碳过渡金属硫化物（TMD）、二维过渡金属碳化物、二维过渡金属碳氮化物（MXene）、过渡金属氧化物、过渡金属氢氧化物。
对于从含层状结构的二维材料中通过剥离制备出二维纳米片的具体方式，其通常可以为，首先将块状（或粉末状）的含层状结构的二维材料磨碎，然后将其颗粒分散于第二有机溶剂中，之后通过超声剥离，从而生成出二维纳米片，为了使二维纳米片分能够从含层状结构的二维材料中进行剥离，在通过超声剥离过程中，超声频率可以为15~60kHz、超声功率可以为300~1800W以及超声时长可以为20~720min。比如，以频率为40kHz、功率为1500W进行超声震荡200min。其中，第二有机溶剂具体包括如下任意一种：二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮、无水乙醇。
在超声剥离之后，通常还需要进行离心清洗，并将离心清洗后的产物进行真空干燥，从而最终得到二维纳米片。在离心洗涤过程中，离心速度可以为4000~10000rpm，离心时长可以为5~40min，所使用的溶剂可以为无水乙醇、丙醇等。
另外，通常还可以采用机械剥离或电化学剥离等方式，从含层状结构的二维材料中剥离出二维纳米片。这里对具体剥离方式不做限定。
步骤S12：将二维纳米片分散于第一有机溶剂中以制备出分散液。
其具体方式可以为，称取一定量的二维纳米片并投入第一有机溶剂中，然后利用电磁搅拌或超声震荡，将二维纳米片分散于第一有机溶剂中，从而制备出分散液。其中，该第一有机溶剂通常可以为具有还原性的有机溶剂，从而能够更好的在后续反应中的对金属离子进行还原，比如，该第一有机溶剂具体可以为N，N-二甲基甲酰胺。
比如，称取50mg的二维纳米片投入200mL的N，N-二甲基甲酰胺中，然后以频率为50kHz、功率为1700W进行超声震荡300min，从而制备出该分散液。
步骤S13：将有机铂盐和其他过渡金属盐溶解于第一有机溶剂中，以制备出混合盐溶液。
其中，这里的有机铂盐通常能够溶解于第一有机溶剂中，比如其可以为乙酰丙酮铂。
对于其他过渡金属盐，其阳离子为除Pt外的过渡金属的阳离子，比如可以为Co、Ni、Fe、Cu、Mo、W或其他过渡金属的阳离子，对于阳离子的价态并不限定，比如可以为2+、3+或5+等。另外，对于其他过渡金属盐，其阴离子可以为硫酸根、硝酸根、氯离子或其他阴离子等。比如，该其他过渡金属盐为Co、Ni、Fe、Cu、Mo或W的盐酸盐，硫酸盐或硝酸盐。另外，考虑到其他过渡金属盐在第一有机溶剂中的溶解度，该其他过渡金属盐也可以为其他过渡金属的有机盐，比如为其他过渡金属的乙酰丙酮盐。
对于所配制出的混合盐溶液，有机铂盐与其他过渡金属盐的摩尔浓度的总和可以为：1.0~100.0mM（毫摩尔每升，mmol/L），比如为1mM、10mM、17mM、30mM、100mM或者介于1.0mM至100.0mM之间的其他浓度。
当然，对于有机铂盐与其他过渡金属盐的浓度，两者之间的摩尔浓度比可以为：0.1：1~1：1。
步骤S14：按指定摩尔比将混合盐溶液与分散液进行混合。
在步骤S12制备出分散液和步骤S13制备出混合盐溶液之后，可以按指定摩尔比将两者进行混合，从而得到混合液。通常为了使两者进行充分的混合，可以通过磁力搅拌、机械搅拌等方式对混合液进行充分搅拌。
其中，指定摩尔比可以具体为二维纳米片与金属盐前驱体的摩尔比为1：0.1~1：5，其中：金属盐前驱体的物质的量具体为有机铂盐与其他过渡金属盐物质的量之和。比如，二维纳米片与金属盐前驱体的摩尔比为1：0.1、1：0.3、1：0.5、1：0.8、1：1、1：1.2、1：1.5、1：1.7、1：2、1：2.4、1：2.8、1：3、1：3.5、1：4、1：4.4、1：4.6、1：4.9、1：5或者介于1：0.1至1：5之间的其他值。
在实际应用中，当二维纳米片与金属盐前驱体的摩尔比较小（比如在接近于1：5左右）时，此时金属盐前驱体的比例相对较高，在二维纳米片上的负载量也相对较多，但也会出现较多的金属盐前驱体未负载的情况，从而导致部分金属盐前驱体的浪费；相反，当二维纳米片与金属盐前驱体的摩尔比较大（比如在接近于1：0.1左右）时，此时金属盐前驱体的比例相对较低，但也可能导致二维纳米片上的负载量相对较少。因此，对于二维纳米片与金属盐前驱体的摩尔比，可以进一步为1：0.3~1:1.5。
步骤S15：将混合液在保护气体氛围下，以预设反应温度进行反应，制得复合纳米材料。
其中，保护气体可以包括氩气、氮气或氦气等。通常可以预先向反应器中通入一定量的保护气体，以排出反应器中的空气，防止空气中的氧气对反应造成干扰。比如，可以预先向反应器中通入30min的氮气，从而在反应器内形成氮气氛围。
对于该预设反应温度，其具体可以为80~200℃。比如为80℃、90℃、100℃、140℃、200℃或介于80℃至200℃之间的其他温度。
另外，对于该反应的反应时长，其可以为10~480min，比如为260min。
需要说明的是，对于该反应所制得的反应产物，可以先通过过滤或离心分离来获得。对于所获得的反应产物，还可以将其再通过超声震荡分散于无水乙醇中，然后进行离心洗涤，并重复超声震荡和离心洗涤2~3次，从而对反应产物进行清洗，其中，超声震荡时的超声频率为15~60kHz以及超声时长为1~3min；离心洗涤时的离心转速为6000~10000rpm/min以及离心时长为5~15min。之后，可以将最终离心洗涤后的反应产物置于真空干燥箱内进行干燥，干燥后得到所制得复合纳米材料。
采用本申请实施例所提供的制备方法，将二维纳米片分散于第一有机溶剂中以制备出分散液，并将有机铂盐和其他过渡金属盐溶解于所述第一有机溶剂以制备出混合盐溶液，然后按指定摩尔比将混合盐溶液与分散液进行混合，之后将混合液在保护气体氛围下，以预设反应温度进行反应，从而制得复合纳米材料。通过该制备方法，能够制备出二维纳米片/铂基合金复合纳米材料作为制氢的高效催化剂，有利于促进反应物的化学吸附与活化，提升制氢反应使得催化性能，从而提高制氢效率以降低能耗。
本申请所提供的该制备方法，主要通过水热法在二维纳米片上生长铂基合金纳米颗粒，相对于直接以金属铂作为制氢时的催化剂，还大大减少了铂在催化剂中的含量，降低了成本；另一方面，该制备方法工艺流程简单、重复性好，所得到的复合纳米材料结构稳定，有利于促进反应物的化学吸附与活化，提升催化性能。
并且所制备的复合纳米材料中，以二维纳米片作为催化剂的载体，铂基合金作为活性位点，由于作为载体的二维纳米片具有极大大的比表面积，有利于反应物的扩散，能够暴露出更多的活性位点，有利于界面电荷的快速转移，提升制氢反应使得催化性能。
在实际应用中，可以将本申请所提供的制备方法所制备出的复合纳米材料，直接作为电解水制氢的催化剂，从而提高制氢效率，也可以向该复合纳米材料中再次加入其它的助催化剂，或者将该复合纳米材料添加至其它的催化剂中，从而催化性能进行改进，均在本申请的保护范围之内。
另外，对于该制备方法的各个步骤，其中，通过步骤S11和步骤S12主要用于制备出二维纳米片的分散液，通过步骤S13制备出混合盐溶液，因此可以不对这两个过程的执行顺序进行限定。比如，可以先通过步骤S11和步骤S12来制备出二维纳米片的分散液，然后通过步骤S13制备出混合盐溶液，也可以先通过步骤S13制备出混合盐溶液，然后通过步骤S11和步骤S12来制备出二维纳米片的分散液，也可以同步制备。
为了便于说明本申请所提供的制备方法所制备出的复合纳米材料的效果，下面可以结合具体实施例进行说明。
实施例1
采用黑磷作为含层状结构的二维材料，从而制备出二维纳米片。并且，有机铂盐为乙酰丙酮铂；其他过渡金属盐为乙酰丙酮铜。三者之间的摩尔比为：二维纳米片（称之为，二维黑磷纳米片）：乙酰丙酮铂：乙酰丙酮铜=1：0.25：0.25。
具体制备步骤如下：
（1）将块体黑磷磨碎分散于N-甲基吡咯烷酮中超声剥离，超声频率为20kHz，超声时长为600min；超声结束后以5000rpm/min进行离心分离，时间为15min，取上清液以转速12000rpm/min离心15min，将沉淀物重新分散在无水级的N，N-二甲基甲酰胺得到二维纳米片的分散液。
（2）以N，N-二甲基甲酰胺为溶剂，乙酰丙酮铂和乙酰丙酮铜为溶质来配制混合盐溶液，其中乙酰丙酮铂和乙酰丙酮铜的摩尔比为0.25：0.25。
（3）按二维黑磷纳米片：乙酰丙酮铂：乙酰丙酮铜的摩尔比为1：0.25：0.25，将分散液与混合盐溶液混合均匀，所得混合液放入聚四氟乙烯密封反应管中，在惰性气体保护条件下加热至180℃，并保持240min，反应结束后用无水乙醇进行多次离心清洗，即可得到所制备出的复合纳米材料（称之为二维黑磷纳米片/铂铜合金复合纳米材料）。如图2所示为该二维黑磷纳米片/铂铜合金复合纳米材料的透射电镜示意图，其中，片层状结构为二维黑磷纳米片，黑色颗粒为铂铜合金。
利用二维黑磷纳米片表面少量的磷氧键和加热后的N，N-二甲基甲酰胺将金属盐前驱体还原为金属单质。铂基合金复合结构的存在,有利于制氢反应物的扩散和活性位点的暴露,且各组分之间具有协同催化效应,有利于制氢反应时催化性能的提高。
实施例2
采用石墨作为含层状结构的二维材料，从而制备出二维纳米片（称之为，石墨烯纳米片）。并且，有机铂盐为乙酰丙酮铂；其他过渡金属盐为乙酰丙酮铜。三者之间的摩尔比为：石墨烯纳米片：乙酰丙酮铂：乙酰丙酮铜=1：0.25：0.25。
具体制备步骤如下：
（1）将石墨粉末分散于N-甲基吡咯烷酮中超声剥离，超声频率为20kHz，超声时长为600min；超声结束后以5000rpm/min进行离心分离，时间为15min，取上清液以转速12000rpm/min离心15min，将沉淀物重新分散在无水级的N，N-二甲基甲酰胺中，从而制得二维纳米片的分散液。
（2）以N，N-二甲基甲酰胺为溶剂，乙酰丙酮铂和乙酰丙酮铜为溶质来配制混合盐溶液，其中乙酰丙酮铂和乙酰丙酮铜的摩尔比为0.25：0.25。
（3）按石墨烯纳米片：乙酰丙酮铂：乙酰丙酮铜的摩尔比为1：0.25：0.25，将分散液与混合盐溶液混合均匀，所得混合液放入聚四氟乙烯密封反应管中，在惰性气体保护条件下加热至180℃，保持240min，反应结束后用无水乙醇进行多次离心清洗，即可得到所制备出的复合纳米材料（称之为石墨烯纳米片/铂铜合金复合纳米材料）。如图3所示为该石墨烯纳米片/铂铜合金复合纳米材料的透射电镜示意图，其中，片层状结构为石墨烯纳米片，黑色颗粒为铂铜合金。
实施例3
采用二硫化钼作为含层状结构的二维材料，从而制备出二维纳米片。并且，有机铂盐为乙酰丙酮铂；其他过渡金属盐为乙酰丙酮铜。三者之间的摩尔比为：二维纳米片（称之为，二维二硫化钼纳米片）：乙酰丙酮铂：乙酰丙酮铜=1：0.25：0.25。
具体制备步骤如下：
（1）将二硫化钼粉末分散于N-甲基吡咯烷酮中超声剥离，超声频率为20kHz，超声时长为600min；超声结束后以5000rpm/min进行离心分离，时间为15min，取上清液以转速12000rpm/min离心15min，将沉淀物重新分散在无水级的N，N-二甲基甲酰胺中，从而制得二维纳米片的分散液。
（2）以N，N-二甲基甲酰胺为溶剂，乙酰丙酮铂和乙酰丙酮铜为溶质来配制混合盐溶液，其中乙酰丙酮铂和乙酰丙酮铜的摩尔比为0.25：0.25。
（3）按二维二硫化钼纳米片：乙酰丙酮铂：乙酰丙酮铜的摩尔比为1：0.25：0.25，将分散液与混合盐溶液混合均匀，所得混合液放入聚四氟乙烯密封反应管中，在惰性气体保护条件下加热至180℃，保持240min，反应结束后用无水乙醇进行多次离心清洗，即可得到所制备出的复合纳米材料（称之为二维二硫化钼纳米片/铂铜合金复合纳米材料）。如图4所示为该二维二硫化钼纳米片/铂铜合金复合纳米材料的透射电镜示意图，其中，片层状结构为二维二硫化钼纳米片，黑色颗粒为铂铜合金。
图5为本申请上述的实施例1~3所制备出的二维黑磷纳米片/铂铜合金复合纳米材料（BP-PtCu）、石墨烯纳米片/铂铜合金复合纳米材料（G-PtCu）、二维二硫化钼纳米片/铂铜合金复合纳米材料（MoS 2-PtCu），在相同测试条件下的酸性析氢反应性能测试图，其中，横坐标为可逆氢电极（reversible hydrogen electrode，RHE，其单位为V），纵坐标为电流密度（Current Density，单位为mA cm -2）。并且，对比例为采用纯石墨电极（C），也在相同测试条件下的酸性析氢反应性能测试图。从该图5中可以看出，G-PtCu性能最佳，BP-PtCu其次，MoS 2-PtCu性能最差，但这三种材料均比纯石墨电极（C）的析氢性能更好。
此外，在实际应用中，综合考虑到制备成本和催化性能，可以选取某些既符合成本需求，也符合催化性能需求的二维纳米片作为载体，从而制备出相应的复合纳米材料作为电解水制氢的催化剂。比如，考虑到石墨烯纳米片的成本较高，但同时催化性能较佳，当需要高催化性能的催化剂时，可以选取石墨烯纳米片作为载体。并且，该石墨烯纳米片较优的可以采用本申请实施例中的方法，将石墨粉末分散于N-甲基吡咯烷酮中超声剥离制得，其超声频率可以为15~60kHz、超声功率可以为300~1800W以及超声时长可以为20~720min。
需要说明的是，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、商品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、商品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括要素的过程、方法、商品或者设备中还存在另外的相同要素。
以上仅为本申请的实施例而已，并不用于限制本申请。对于本领域技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原理之内所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。

Claims (10)

  1. 一种复合纳米材料的制备方法，其特征在于，包括：
    将二维纳米片分散于第一有机溶剂中以制备出分散液，并将有机铂盐和其他过渡金属盐溶解于所述第一有机溶剂以制备出混合盐溶液；
    按指定摩尔比将所述混合盐溶液与所述分散液进行混合；
    将混合液在保护气体氛围下，以预设反应温度进行反应，制得复合纳米材料。
  2. 如权利要求1所述的制备方法，其特征在于，所述二维纳米片，具体包括如下任意一种或多种：石墨烯纳米片、二维二硫化钼纳米片、二维黑磷纳米片、二维六方氮化硼的纳米片、二维类石墨相氮化碳的纳米片、二维过渡金属硫化物的纳米片、二维过渡金属碳化物的纳米片、二维过渡金属碳氮化物的纳米片、二维过渡金属氧化物的纳米片、二维过渡金属氢氧化物的纳米片。
  3. 如权利要求1所述的制备方法，其特征在于，所述方法还包括：
    将含层状结构的二维材料的颗粒分散于第二有机溶剂中，并通过超声剥离以生成所述二维纳米片。
  4. 如权利要求3所述的制备方法，其特征在于，所述第一有机溶剂具体包括：还原性的有机溶剂；以及，
    所述第二有机溶剂具体包括如下任意一种：二甲基亚砜、N，N-二甲基甲酰胺、N-甲基吡咯烷酮、无水乙醇。
  5. 如权利要求2所述的制备方法，其特征在于，在通过超声剥离以生成所述二维纳米片过程中，超声频率为15~60kHz、超声功率为300~1800W以及超声时长为20~720min。
  6. 如权利要求1所述的制备方法，其特征在于，
    所述有机铂盐具体包括：乙酰丙酮铂；以及，
    所述其他过渡金属盐具体包括：Co、Ni、Fe、Cu、Mo或W的盐酸盐、硫酸盐、硝酸盐或乙酰丙酮盐。
  7. 如权利要求1所述的制备方法，其特征在于，在所述混合盐溶液中，有机铂盐与其他过渡金属盐的摩尔浓度的总和为：1.0~100.0mM；以及，
    在所述混合盐溶液中，有机铂盐与其他过渡金属盐的摩尔比为：0.1：1~1：1。
  8. 如权利要求1所述的制备方法，其特征在于，所述指定摩尔比具体包括：所述二维纳米片与金属盐前驱体的摩尔比为：1：0.1~1：5，其中：金属盐前驱体的物质的量具体为有机铂盐与其他过渡金属盐物质的量之和。
  9. 一种复合纳米材料，其特征在于，所述的复合纳米材料采用如权利要求1~8中任意一项所述的方法进行制备得到。
  10. 一种电解水制氢的催化剂，其特征在于，所述催化剂中包括如权利要求1~8中任意一项所述的方法所制备出的复合纳米材料。
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