WO2020248245A1 - Monoatomic material, preparation method and use thereof - Google Patents

Monoatomic material, preparation method and use thereof Download PDF

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WO2020248245A1
WO2020248245A1 PCT/CN2019/091353 CN2019091353W WO2020248245A1 WO 2020248245 A1 WO2020248245 A1 WO 2020248245A1 CN 2019091353 W CN2019091353 W CN 2019091353W WO 2020248245 A1 WO2020248245 A1 WO 2020248245A1
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optionally
monoatomic
plasma
precursor
hydrogen evolution
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PCT/CN2019/091353
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French (fr)
Chinese (zh)
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刘碧录
罗雨婷
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清华-伯克利深圳学院筹备办公室
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Priority to PCT/CN2019/091353 priority Critical patent/WO2020248245A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • 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
    • 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 belongs to the technical field of monoatomic materials, and relates to a monoatomic material, its preparation method and application.
  • monoatomic materials are mainly achieved by thermal diffusion, in-situ pyrolysis, template synthesis or ion exchange methods. These monoatomic materials are limited to the form of powder or mesoporous materials, which limits their application in some fields.
  • CN109225257A discloses a supported single-atom catalyst and its preparation method.
  • the catalyst is composed of monodisperse metal atoms uniformly supported on the surface of the nano-substrate material.
  • the preparation method includes: adopting a three-electrode system for electrochemical deposition in an electrolyte solution containing metal salts, using a glassy carbon electrode loaded with nano-substrate material as a working electrode, a graphite rod as a counter electrode, and a silver/silver chloride electrode As a reference electrode, linear voltammetric scanning is performed to make metal atoms monodisperse and uniformly deposit on the nano-substrate material to obtain the supported single-atom catalyst.
  • CN109126774A discloses an ultra-highly dispersed supported monoatom noble metal catalyst and a preparation method thereof.
  • the preparation method includes: dissolving the metal precursor in water or ethanol, immersing the obtained solution on the carrier, evaporating the solvent in a water bath, drying in an oven, roasting under N protection, or reduction in an H atmosphere; CO and pumped
  • the halogenated alkane is preheated, vaporized and mixed, and then enters the tubular reactor equipped with the roasted or reduced granular or powdered catalyst.
  • the catalyst is first raised to the treatment temperature under the protection of the N atmosphere, and then switched to a mixed gas of CO and halogenated alkane After the treatment, the N protection is reduced to room temperature to obtain a supported monoatomic noble metal catalyst.
  • This application prepares monoatomic materials by applying plasma treatment to the precursors.
  • the method is efficient and universal. It can realize the controllable preparation of monoatomic materials and the high-load preparation of monoatoms, showing good application prospects.
  • One of the objectives of this application is to provide a method for preparing monoatomic materials, the method comprising the following steps:
  • the precursor is processed by plasma to obtain a monoatomic material, and the elements in the monoatomic material include metal elements.
  • This application creatively proposes the use of plasma to prepare monoatomic materials containing metal elements, which is suitable for different forms of load substrates and has universal applicability to different metal elements.
  • the method of this application is applicable to the preparation of monoatomic materials of all metal elements. , Especially can be used to realize the preparation of two or more different metal element monoatomic materials. In addition, this method has the advantage of being fast and simple.
  • This application realizes the controllable preparation of a series of monoatomic materials by controlling the gas flow rate, reaction time and temperature of the protective atmosphere introduced.
  • the precursor includes any one or a combination of at least two of metal oxides, metal chalcogenides, metal phosphides, metal halides, and metal carbides.
  • the metal element in the precursor includes any one or a combination of at least two of molybdenum, tungsten, platinum, indium, iron, niobium, gold, cobalt, nickel, manganese, chromium and bismuth.
  • the metal elements in the precursors described in this application include all main group metal elements and sub-group metal elements, including but not limited to molybdenum, tungsten, platinum, indium, iron, niobium, gold, cobalt, nickel, manganese, chromium and bismuth Any one or a combination of at least two of them.
  • the morphology of the precursor includes any one or a combination of at least two of bulk material, powder material, thin film material and mesoporous material.
  • the process, the plasma processing of the precursor, the degree of vacuum of the reaction chamber is 10 -9 mbar ⁇ 10 2 mbar, optionally 10 -2 ⁇ 10 2 mbar, for example 10 -8 mbar, 10 - 7 mbar, 10 -6 mbar, 10 -5 mbar, 10 -4 mbar, 10 -3 mbar, 10 -2 mbar, 10 -1 mbar, 10 0 mbar, 1.5mbar or the like 10mbar.
  • the reaction temperature is -100°C to 1500°C, for example -80°C, -60°C, -50°C, -20°C, 0°C, 20°C, 30°C , 50°C, 60°C, 80°C, 100°C, 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 1000°C or 1200°C etc.
  • the metal element in the precursor includes molybdenum and/or tungsten
  • the reaction temperature is ⁇ 200°C, such as -80°C, -60°C, -50°C, -20°C, 0°C, 20°C, 30°C, 50°C, 60°C, 80°C, 100°C, 120°C, 130°C, 150°C, 160°C or 180°C etc.
  • the reaction temperature is ⁇ 200°C, and if the temperature is greater than 200°C, agglomeration of single atoms will result.
  • the metal element in the precursor includes iron and/or bismuth
  • the reaction temperature is ⁇ 150°C, for example -80°C, -60°C, -50°C, -20°C, 0°C, 20°C, 30°C, 50°C, 60°C, 80°C, 100°C, 120°C or 130°C etc.
  • the reaction temperature is less than or equal to 150°C, and if the temperature is greater than 150°C, agglomeration of single atoms will result.
  • the reaction time is 2s-20h, optionally 5s-60min, optionally 40s-240s, such as 5s, 10s, 20s, 50s, 60s, 80s, 100s , 120s, 150s, 180s, 200s, 220s, 240s, 280s, 300s, 400s, 500s, 600s, 800s, 1000s, 1500s, 2000s, 3000s, 1h, 2h, 5h, 6h, 8h, 10h, 12h, 15h or 18h Wait.
  • 5s, 10s, 20s, 50s, 60s, 80s 100s , 120s, 150s, 180s, 200s, 220s, 240s, 280s, 300s, 400s, 500s, 600s, 800s, 1000s, 1500s, 2000s, 3000s, 1h, 2h, 5h, 6h, 8h, 10h, 12h, 15h or 18h Wait.
  • the preparation process of the plasma includes: exciting gas to generate plasma.
  • the vacuum degree of the reaction chamber is 10 -9 mbar to 10 2 mbar, optionally 10 -2 to 10 2 mbar, such as 10 -8 mbar, 10 -7 mbar, 10 -6 mbar, 10 -5 mbar, 10 -4 mbar, 10 -3 mbar, 10 -2 mbar, 10 -1 mbar, 10 0 mbar, 1.5mbar or the like 10mbar.
  • the gas used includes any one or a combination of at least two of air, oxygen, hydrogen, argon, methane, nitrogen, and ammonia.
  • the gas flow rate is 5 sccm to 1000 sccm, for example, 10 sccm, 20 sccm, 50 sccm, 80 sccm, 100 sccm, 200 sccm, 300 sccm, 400 sccm, 500 sccm, 600 sccm, 700 sccm, 800 sccm, 900 sccm, etc.
  • the time for introducing the gas is 1 min to 60 min, for example, 5 min, 8 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 50 min or 55 min.
  • the AC power frequency used to excite the plasma is 50 Hz to 100 MHz, optionally 10 kHz to 200 kHz, such as 100 Hz, 200 Hz, 500 Hz, 1 kHz, 2 kHz, 5 kHz, 10 kHz, 20 kHz, 50 kHz, 80 kHz, 100 kHz, 150 kHz , 200kHz, 500kHz, 1MHz, 5MHz, 10MHz, 20MHz, 50MHz, 70MHz or 80MHz etc.
  • the DC discharge voltage used to excite the plasma is 1V-1000V, for example, 5V, 10V, 20V, 50V, 80V, 100V, 200V, 400V, 500V, 600V or 800V.
  • the preparation method of a monoatomic material described in this application includes the following steps:
  • the plasma is excited by an AC power source with a frequency of 10 kHz to 200 kHz, the precursor is treated by plasma, and the reaction temperature is controlled to be -100° C. to 1500° C., and the processing time is 40 s to 240 s to obtain monoatomic materials.
  • the second objective of this application is to provide a monoatomic material, which is obtained by the preparation method described in one of the objectives.
  • the element type in the monoatomic material is ⁇ 1, may be 1-10, may be 1-5, and may be 1-3, such as 2, 3, 4, 5, 6, 7, 8 , 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 etc.
  • the preparation method of the present application can realize the preparation of a single atom of a single element and a single atom of multiple elements.
  • the monoatomic material includes a supported type and/or a lattice embedded type.
  • the supported monoatomic material of the present application is a metal single atom supported on a carrier; the lattice embedded monoatomic material of the present application is a metal single atom embedded in the carrier.
  • the third object of the application is to provide a use of the monoatomic material as described in the second object, which is used for any one or a combination of at least two of the hydrogen evolution electrocatalyst, photodetector and electronic device .
  • the fourth object of the present application is to provide a hydrogen evolution electrocatalyst, which includes the monoatomic material described in the second object.
  • the hydrogen evolution electrocatalyst prepared in this application can be used to catalyze the hydrogen evolution of acidic and alkaline electrolysis of water at the same time, and the current density during hydrogen production can reach 2A/cm 2 , so that it can better adapt to the industrial level of high current density electrolysis of water to produce hydrogen.
  • the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of acidic electrolyzed water, and the hydrogen production current density is 0.001A/cm 2 ⁇ 2A/cm 2 , for example, 0.01A/cm 2 , 0.05A/cm 2 , 0.1A/cm 2 , 0.2A/cm 2 , 0.3A/cm 2 , 0.4A/cm 2 , 0.5A/cm 2 , 0.6A/cm 2 , 0.7A/cm 2 , 0.8A/cm 2 or 0.9A/cm 2, etc.
  • the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of acidic electrolyzed water
  • the acidic solution used is 0.5-1 mol/L sulfuric acid
  • the hydrogen evolution electrocatalyst has a hydrogen production current density of 0.001 A/cm 2 to 0.4 A/cm 2 .
  • the potential is 200mV ⁇ 270mV; the sulfuric acid concentration is 0.6mol/L, 0.7mol/L, 0.8mol/L or 0.9mol/L, etc.; the hydrogen production current density is, for example, 0.01A/cm 2 , 0.05A/cm 2 , 0.1A/cm 2 , 0.15A/cm 2 , 0.2A/cm 2 , 0.25A/cm 2 , 0.3A/cm 2 or 0.35A/cm 2, etc.; the overpotential is for example 210mV, 220mV, 230mV, 240mV , 250mV or 260mV, etc.
  • the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of alkaline water electrolysis, and the hydrogen production current density is 0.001A/cm 2 ⁇ 2A/cm 2 , for example, 0.01A/cm 2 , 0.05A/cm 2 , 0.1A/cm 2 , 0.2A/cm 2 , 0.3A/cm 2 , 0.4A/cm 2 , 0.5A/cm 2 , 0.6A/cm 2 , 0.7A/cm 2 , 0.8A/cm 2 or 0.9A/cm 2, etc.
  • the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of alkaline electrolyzed water
  • the adopted alkaline solution includes potassium hydroxide and/or sodium hydroxide.
  • the alkaline solution is 0.5 to 1 mol/L potassium hydroxide aqueous solution
  • the hydrogen production current density is 0.001 A/cm 2 to 0.4 A/cm 2
  • the overpotential is 200 mV to 300 mV.
  • the concentration of the alkaline solution is 0.6 mol/L, 0.7 mol/L, 0.8 mol/L or 0.9 mol/L, etc.
  • the hydrogen production current density is, for example, 0.01 A/cm 2 , 0.05 A/cm 2 , 0.1 A/ cm 2 , 0.15A/cm 2 , 0.2A/cm 2 , 0.25A/cm 2 , 0.3A/cm 2 or 0.35A/cm 2, etc.
  • the overpotential is for example 210mV, 220mV, 230mV, 240mV, 250mV, 260mV , 270mV, 280mV or 290mV, etc.
  • This application creatively proposes the use of plasma to prepare metal element-containing monoatomic materials, which is suitable for different forms of load substrates and has universal applicability to different metal elements.
  • the method of this application can be applied to all metal elements.
  • the preparation of atomic materials is particularly applicable to the preparation of two or more different metal element monoatomic materials.
  • the method has the advantages of rapidness and simplicity.
  • This application realizes the controllable preparation of a series of monoatomic materials by controlling the gas type and flow rate, reaction time and temperature of the introduced reaction atmosphere.
  • the hydrogen evolution electrocatalyst prepared in this application can be used to catalyze the hydrogen evolution of acidic and alkaline electrolysis of water at the same time, and the current density during hydrogen production can reach 2A/cm 2 , so as to better adapt to the industrial level of high current density electrolysis of aquatic products hydrogen.
  • FIG. 1 is a schematic diagram of a method for preparing monoatomic materials using plasma technology in this application;
  • Example 2 is a transmission electron microscope image of the molybdenum monoatomic material prepared in Example 1 of this application;
  • FIG. 3 is a transmission electron microscope image of a type-molybdenum monoatomic material prepared in Example 1 of this application;
  • Fig. 4 is a simulation diagram of a type-molybdenum monoatomic material prepared in Example 1 of this application;
  • Fig. 5 is a plan view of the intensity of a single molybdenum atom of type 1 prepared in Example 1 of the application;
  • Fig. 6 is a transmission electron microscope image of the type di-molybdenum monoatomic material prepared in Example 1 of the application;
  • Fig. 7 is a simulation diagram of the type di-molybdenum monoatomic material prepared in Example 1 of the application;
  • Fig. 8 is a plan view of the strength of the type di-molybdenum single atom prepared in Example 1 of the application;
  • Example 10 is a transmission electron microscope image of Type 1 and Type 2 tungsten monoatomic materials prepared in Example 4 of this application;
  • Example 11 is a simulation diagram of Type 1 and Type 2 tungsten single-atom materials prepared in Example 4 of this application;
  • Example 13 is a plan view of the strength of a single atom of type two tungsten prepared in Example 4 of the application;
  • Fig. 14 is a current density-overpotential curve diagram of the hydrogen evolution reaction of the monoatomic material prepared in Example 1 of the application in a 0.5 mol/L sulfuric acid aqueous solution;
  • FIG. 15 is a current density-overpotential curve diagram of the hydrogen evolution reaction of the monoatomic material prepared in Example 1 of the application in a 1.0 mol/L potassium hydroxide aqueous solution.
  • FIG. 1 The schematic diagram of the method for preparing monoatomic materials by plasma technology in the examples of this application is shown in FIG. 1, and the precursor in the figure is the precursor described in this application. It should be understood by those skilled in the art that the described embodiments are only to help understand the application and should not be regarded as specific limitations to the application.
  • a preparation method of monoatomic material includes the following steps:
  • Figure 2 is an atomically resolved transmission electron microscope image of the molybdenum monoatomic material.
  • Figures 3 and 4 are respectively a transmission electron microscope image of the molybdenum monoatomic material of type one and its simulation diagram. It can be seen from the figure that the obtained molybdenum The single-atom load is high and the distribution is uniform;
  • Figure 5 is a plan view of the intensity of a single molybdenum atom of type one;
  • the transmission electron microscope image of a single-atom molybdenum atom of type two and its simulation are shown in Figure 6 and Figure 7, respectively, and
  • Figure 8 It is a plan view of the strength of a type of molybdenum monoatom. It can be seen from Figures 2-8 that the prepared monoatomic material is a molybdenum monoatomic material supported on a molybdenum disulfide precursor.
  • the molybdenum monoatomic material obtained in this example was used as a catalyst for the hydrogen evolution reaction of electrolyzed water.
  • the current density of the molybdenum monoatomic material in the 0.5mol/L sulfuric acid aqueous solution and 1.0mol/L potassium hydroxide aqueous solution respectively The overpotential curves are shown in Figure 14 and Figure 15, respectively.
  • the molybdenum single atom/molybdenum disulfide composite system in the figure is the molybdenum single atom supported on the molybdenum disulfide precursor as a catalyst in this example.
  • the platinum in the figure is commercial platinum
  • the catalyst, molybdenum disulfide is a commercial molybdenum disulfide catalyst. It can be seen from Figure 14 and Figure 15 that the obtained monoatomic material has good activity when used as an electrocatalyst for hydrogen evolution in acidic or alkaline solutions.
  • the difference from Embodiment 1 is that the plasma treatment time in step (3) is 160s.
  • step (3) an AC power source with a frequency of 20 kHz is used to excite the plasma, the precursor is treated with plasma, the reaction temperature is controlled to 200° C., and the treatment time is 240 s to obtain a molybdenum monoatomic material.
  • step (1) the monoatomic layer molybdenum disulfide precursor is replaced with a monoatomic layer tungsten disulfide precursor to obtain a tungsten monoatomic material.
  • Figure 9 is an atomically resolved transmission electron microscope image of the tungsten single-atom material. It can be seen from the figure that the prepared tungsten single-atom has a high loading and uniform distribution; Figures 10 and 11 are type one (the figure is Tungsten single atom 1) and type 2 (tungsten single atom 2 in the figure) of tungsten single atom transmission electron microscope images and their simulation images; Figures 12 and 13 are type 1 (tungsten single atom 1 in the figure) and type 2 respectively (The figure shows the tungsten single atom 2) the plan view of the tungsten single-atom strength; comprehensively shown in Figures 9-13, the prepared single-atom material is a tungsten single-atom material supported on a tungsten disulfide precursor, and There are two types of location: Type One and Type Two.
  • a preparation method of monoatomic material includes the following steps:
  • a preparation method of monoatomic material includes the following steps:
  • the plasma is excited by an AC power source with a frequency of 22 kHz, the precursor is treated by plasma, the reaction temperature is controlled to 50° C., and the treatment time is 240 s to obtain a molybdenum monoatomic material.
  • a preparation method of monoatomic material includes the following steps:
  • a preparation method of monoatomic material includes the following steps:
  • V 0.1 Mo 0.9 S 2 vanadium disulfide-molybdenum alloy
  • the plasma is excited by an AC power source with a frequency of 100kHz, the precursor is treated by plasma, the reaction temperature is controlled at 100°C, and the treatment time is 160s, to obtain a monoatomic material of molybdenum and vanadium, namely molybdenum monoatom and Vanadium single atom.
  • the plasma is excited by an AC power source with a frequency of 22kHz, and the precursor is treated by plasma.
  • the reaction temperature is controlled to 120°C and the treatment time is 80s to obtain monoatomic materials of tungsten and niobium. Niobium single atom.
  • a preparation method of monoatomic material includes the following steps:
  • the indium selenide precursor in the reaction chamber, the reaction chamber is evacuated to a vacuum of the reaction chamber is 10 0 mbar;
  • a preparation method of monoatomic material includes the following steps:
  • Example 1 To Load (wt%) Example 1 2 Example 2 5 Example 3 1 Example 4 2 Example 5 4 Example 6 2 Example 7 2 Example 8 4 Example 9 3 Example 10 5 Example 11 5 Example 12 4
  • the monoatomic material obtained in this application has a relatively high loading of 1 to 5 wt%, and the preparation of two or more different metal element monoatomic materials can be achieved.

Abstract

Provided are a monoatomic material, a preparation method and use thereof. The method includes the following steps: treating the precursor with plasma to obtain a monoatomic material, the elements in the monoatomic material include metal elements.

Description

一种单原子材料、及其制备方法和用途Monoatomic material, and preparation method and use thereof 技术领域Technical field
本申请属于单原子材料技术领域，涉及一种单原子材料、及其制备方法和用途。This application belongs to the technical field of monoatomic materials, and relates to a monoatomic material, its preparation method and application.
背景技术Background technique
自首次报道以来，单原子材料由于其优异的催化活性、高的活性中心利用率和独特的理化性质，已有众多学者投入到对单原子材料的研究和应用中来。研发高效、普适、高单原子载量的制备方法是目前该领域的重大挑战。Since the first report, due to its excellent catalytic activity, high utilization rate of active centers and unique physical and chemical properties, many scholars have invested in the research and application of monoatomic materials. The research and development of efficient, universal and high single-atom loading preparation methods is a major challenge in this field.
目前，制备单原子材料主要是通过热扩散、原位热解、模板合成或离子交换方法来实现的，这些单原子材料局限于粉末或介孔材料的形式，限制了其在一些领域的应用。At present, the preparation of monoatomic materials is mainly achieved by thermal diffusion, in-situ pyrolysis, template synthesis or ion exchange methods. These monoatomic materials are limited to the form of powder or mesoporous materials, which limits their application in some fields.
CN109225257A公开了一种负载型单原子催化剂及其制备方法。所述催化剂是由单分散金属原子均匀地负载在纳米衬底材料表面构成。其制备方法包括：在包含金属盐的电解质溶液中，采用三电极体系进行电化学沉积，以负载有纳米衬底材料的玻碳电极作为工作电极，石墨棒作为对电极，银/氯化银电极作为参比电极，进行线性伏安扫描，使金属原子单分散、均匀地沉积到纳米衬底材料上，得到所述负载型单原子催化剂。CN109225257A discloses a supported single-atom catalyst and its preparation method. The catalyst is composed of monodisperse metal atoms uniformly supported on the surface of the nano-substrate material. The preparation method includes: adopting a three-electrode system for electrochemical deposition in an electrolyte solution containing metal salts, using a glassy carbon electrode loaded with nano-substrate material as a working electrode, a graphite rod as a counter electrode, and a silver/silver chloride electrode As a reference electrode, linear voltammetric scanning is performed to make metal atoms monodisperse and uniformly deposit on the nano-substrate material to obtain the supported single-atom catalyst.
CN109126774A公开了一种超高分散负载型单原子贵金属催化剂及其制备方法。所述制备方法包括：将金属前驱体在水或乙醇中溶解，得到的溶液浸渍于载体上，水浴蒸干溶剂，烘箱中烘干，N保护下焙烧，或H气氛还原；CO和泵入的卤代烷烃预热汽化混合后进入到装有焙烧或还原后的颗粒状或粉末状催化剂的管式反应器中，催化剂首先在N气氛保护下升至处理温度，然后切换成 CO和卤代烷烃混合气处理，处理后在N保护下降至室温，得到负载型单原子贵金属催化剂。CN109126774A discloses an ultra-highly dispersed supported monoatom noble metal catalyst and a preparation method thereof. The preparation method includes: dissolving the metal precursor in water or ethanol, immersing the obtained solution on the carrier, evaporating the solvent in a water bath, drying in an oven, roasting under N protection, or reduction in an H atmosphere; CO and pumped The halogenated alkane is preheated, vaporized and mixed, and then enters the tubular reactor equipped with the roasted or reduced granular or powdered catalyst. The catalyst is first raised to the treatment temperature under the protection of the N atmosphere, and then switched to a mixed gas of CO and halogenated alkane After the treatment, the N protection is reduced to room temperature to obtain a supported monoatomic noble metal catalyst.
虽然上述文献对目前的单原子材料的开发提供了一些帮助，但依然存在着单原子材料形式受限、难以实现可控制备、单原子载量不高等问题。因此，如何开发一种具有普适性、高单原子载量的单原子材料制备方法已成为目前亟待解决的问题。Although the above-mentioned documents provide some help for the development of current monoatomic materials, there are still problems such as limited monoatomic materials, difficulty in achieving controllable preparation, and low monoatomic loading. Therefore, how to develop a method for preparing monoatomic materials with universality and high monoatomic loading has become an urgent problem to be solved.
发明内容Summary of the invention
本申请的目的在于提供一种单原子材料、及其制备方法和用途。本申请通过对前驱物采用等离子体处理以制备单原子材料，方法高效、且具有普适性，能实现单原子材料的可控制备和单原子的高载量制备，表现出良好的应用前景。The purpose of this application is to provide a monoatomic material and its preparation method and application. This application prepares monoatomic materials by applying plasma treatment to the precursors. The method is efficient and universal. It can realize the controllable preparation of monoatomic materials and the high-load preparation of monoatoms, showing good application prospects.
为达到此目的，本申请提供如下技术方案：To achieve this goal, this application provides the following technical solutions:
本申请的目的之一在于提供一种单原子材料的制备方法，所述方法包括如下步骤：One of the objectives of this application is to provide a method for preparing monoatomic materials, the method comprising the following steps:
采用等离子体处理前驱物，得到单原子材料，所述单原子材料中的元素包含金属元素。The precursor is processed by plasma to obtain a monoatomic material, and the elements in the monoatomic material include metal elements.
本申请创造性的提出采用等离子体制备含金属元素的单原子材料，适用于不同形式的负载基底，对不同金属元素也具有普适性，本申请的方法可适用于所有金属元素的单原子材料制备，特别是可用于实现两种及以上不同金属元素单原子材料的制备。另外，该方法具有快速、简单的优势。This application creatively proposes the use of plasma to prepare monoatomic materials containing metal elements, which is suitable for different forms of load substrates and has universal applicability to different metal elements. The method of this application is applicable to the preparation of monoatomic materials of all metal elements. , Especially can be used to realize the preparation of two or more different metal element monoatomic materials. In addition, this method has the advantage of being fast and simple.
本申请通过控制通入的保护气氛的气体流量、反应时间和温度，实现一系列单原子材料的可控制备。This application realizes the controllable preparation of a series of monoatomic materials by controlling the gas flow rate, reaction time and temperature of the protective atmosphere introduced.
可选地，所述前驱物包括金属氧化物、金属硫族化合物、金属磷化物、金 属卤化物和金属碳化物中的任意一种或至少两种的组合。Optionally, the precursor includes any one or a combination of at least two of metal oxides, metal chalcogenides, metal phosphides, metal halides, and metal carbides.
可选地，所述前驱物中的金属元素包括钼、钨、铂、铟、铁、铌、金、钴、镍、锰、铬和铋中的任意一种或至少两种的组合。Optionally, the metal element in the precursor includes any one or a combination of at least two of molybdenum, tungsten, platinum, indium, iron, niobium, gold, cobalt, nickel, manganese, chromium and bismuth.
本申请所述前驱物中的金属元素包括所有的主族金属元素和副族金属元素，包括但不限于钼、钨、铂、铟、铁、铌、金、钴、镍、锰、铬和铋中的任意一种或至少两种的组合。The metal elements in the precursors described in this application include all main group metal elements and sub-group metal elements, including but not limited to molybdenum, tungsten, platinum, indium, iron, niobium, gold, cobalt, nickel, manganese, chromium and bismuth Any one or a combination of at least two of them.
可选地，所述前驱物的形貌包括块体材料、粉末材料、薄膜材料和介孔材料中的任意一种或至少两种的组合。Optionally, the morphology of the precursor includes any one or a combination of at least two of bulk material, powder material, thin film material and mesoporous material.
可选地，所述等离子体处理前驱物的过程中，反应腔室的真空度为10 -9mbar～10 2mbar，可选为10 -2～10 2mbar，例如10 -8mbar、10 -7mbar、10 -6mbar、10 -5mbar、10 -4mbar、10 -3mbar、10 -2mbar、10 -1mbar、10 0mbar、1.5mbar或10mbar等。 Optionally the process, the plasma processing of the precursor, the degree of vacuum of the reaction chamber is 10 -9 mbar ~ 10 2 mbar, optionally 10 -2 ~ 10 2 mbar, for example 10 -8 mbar, 10 - 7 mbar, 10 -6 mbar, 10 -5 mbar, 10 -4 mbar, 10 -3 mbar, 10 -2 mbar, 10 -1 mbar, 10 0 mbar, 1.5mbar or the like 10mbar.
可选地，所述等离子体处理前驱物的过程中，反应温度为-100℃～1500℃，例如-80℃、-60℃、-50℃、-20℃、0℃、20℃、30℃、50℃、60℃、80℃、100℃、200℃、300℃、400℃、500℃、600℃、700℃、800℃、1000℃或1200℃等。Optionally, during the plasma treatment of the precursor, the reaction temperature is -100°C to 1500°C, for example -80°C, -60°C, -50°C, -20°C, 0°C, 20°C, 30°C , 50℃, 60℃, 80℃, 100℃, 200℃, 300℃, 400℃, 500℃, 600℃, 700℃, 800℃, 1000℃ or 1200℃ etc.
可选地，所述前驱物中的金属元素包括钼和/或钨，所述反应温度≤200℃，例如-80℃、-60℃、-50℃、-20℃、0℃、20℃、30℃、50℃、60℃、80℃、100℃、120℃、130℃、150℃、160℃或180℃等。Optionally, the metal element in the precursor includes molybdenum and/or tungsten, and the reaction temperature is ≤200°C, such as -80°C, -60°C, -50°C, -20°C, 0°C, 20°C, 30℃, 50℃, 60℃, 80℃, 100℃, 120℃, 130℃, 150℃, 160℃ or 180℃ etc.
本申请所述前驱物中的金属元素包括钼和/或钨时，所述反应温度≤200℃，若温度大于200℃，则会导致单原子的团聚。When the metal element in the precursor described in this application includes molybdenum and/or tungsten, the reaction temperature is ≤200°C, and if the temperature is greater than 200°C, agglomeration of single atoms will result.
可选地，所述前驱物中的金属元素包括铁和/或铋，所述反应温度≤150℃，例如-80℃、-60℃、-50℃、-20℃、0℃、20℃、30℃、50℃、60℃、80℃、100℃、 120℃或130℃等。Optionally, the metal element in the precursor includes iron and/or bismuth, and the reaction temperature is ≤150°C, for example -80°C, -60°C, -50°C, -20°C, 0°C, 20°C, 30℃, 50℃, 60℃, 80℃, 100℃, 120℃ or 130℃ etc.
本申请所述前驱物中的金属元素包括铁和/或铋时，所述反应温度≤150℃，若温度大于150℃，则会导致单原子的团聚。When the metal element in the precursor described in the present application includes iron and/or bismuth, the reaction temperature is less than or equal to 150°C, and if the temperature is greater than 150°C, agglomeration of single atoms will result.
可选地，所述等离子体处理前驱物的过程中，反应时间为2s～20h，可选为5s～60min，可选为40s～240s，例如5s、10s、20s、50s、60s、80s、100s、120s、150s、180s、200s、220s、240s、280s、300s、400s、500s、600s、800s、1000s、1500s、2000s、3000s、1h、2h、5h、6h、8h、10h、12h、15h或18h等。Optionally, during the plasma treatment of the precursor, the reaction time is 2s-20h, optionally 5s-60min, optionally 40s-240s, such as 5s, 10s, 20s, 50s, 60s, 80s, 100s , 120s, 150s, 180s, 200s, 220s, 240s, 280s, 300s, 400s, 500s, 600s, 800s, 1000s, 1500s, 2000s, 3000s, 1h, 2h, 5h, 6h, 8h, 10h, 12h, 15h or 18h Wait.
本申请所述等离子体处理前驱物的过程中，反应时间过长会导致前驱体材料被破坏。During the plasma treatment of the precursors described in the present application, too long a reaction time will cause the precursor materials to be destroyed.
可选地，所述等离子体的制备过程包括：激发气体，生成等离子体。Optionally, the preparation process of the plasma includes: exciting gas to generate plasma.
可选地，所述等离子体制备过程中，反应腔室的真空度为10 -9mbar～10 2mbar，可选为10 -2～10 2mbar，例如10 -8mbar、10 -7mbar、10 -6mbar、10 -5mbar、10 -4mbar、10 -3mbar、10 -2mbar、10 -1mbar、10 0mbar、1.5mbar或10mbar等。 Optionally, during the plasma preparation process, the vacuum degree of the reaction chamber is 10 -9 mbar to 10 2 mbar, optionally 10 -2 to 10 2 mbar, such as 10 -8 mbar, 10 -7 mbar, 10 -6 mbar, 10 -5 mbar, 10 -4 mbar, 10 -3 mbar, 10 -2 mbar, 10 -1 mbar, 10 0 mbar, 1.5mbar or the like 10mbar.
可选地，所述等离子体制备过程中，采用的气体包括空气、氧气、氢气、氩气、甲烷、氮气和氨气中的任意一种或至少两种的组合。Optionally, in the plasma preparation process, the gas used includes any one or a combination of at least two of air, oxygen, hydrogen, argon, methane, nitrogen, and ammonia.
可选地，所述等离子体的制备过程中，气体流速为5sccm～1000sccm，例如10sccm、20sccm、50sccm、80sccm、100sccm、200sccm、300sccm、400sccm、500sccm、600sccm、700sccm、800sccm或900sccm等。Optionally, during the preparation of the plasma, the gas flow rate is 5 sccm to 1000 sccm, for example, 10 sccm, 20 sccm, 50 sccm, 80 sccm, 100 sccm, 200 sccm, 300 sccm, 400 sccm, 500 sccm, 600 sccm, 700 sccm, 800 sccm, 900 sccm, etc.
可选地，所述通入气体的时间为1min～60min，例如5min、8min、10min、15min、20min、25min、30min、35min、40min、50min或55min等。Optionally, the time for introducing the gas is 1 min to 60 min, for example, 5 min, 8 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 50 min or 55 min.
可选地，所述激发等离子体采用的交流电源频率为50Hz～100MHz，可选为10kHz～200kHz，例如100Hz、200Hz、500Hz、1kHz、2kHz、5kHz、10kHz、20kHz、 50kHz、80kHz、100kHz、150kHz、200kHz、500kHz、1MHz、5MHz、10MHz、20MHz、50MHz、70MHz或80MHz等。Optionally, the AC power frequency used to excite the plasma is 50 Hz to 100 MHz, optionally 10 kHz to 200 kHz, such as 100 Hz, 200 Hz, 500 Hz, 1 kHz, 2 kHz, 5 kHz, 10 kHz, 20 kHz, 50 kHz, 80 kHz, 100 kHz, 150 kHz , 200kHz, 500kHz, 1MHz, 5MHz, 10MHz, 20MHz, 50MHz, 70MHz or 80MHz etc.
可选地，所述激发等离子体采用的直流放电电压为1V～1000V，例如5V、10V、20V、50V、80V、100V、200V、400V、500V、600V或800V等。Optionally, the DC discharge voltage used to excite the plasma is 1V-1000V, for example, 5V, 10V, 20V, 50V, 80V, 100V, 200V, 400V, 500V, 600V or 800V.
作为可选技术方案，本申请所述一种单原子材料的制备方法，包括如下步骤：As an optional technical solution, the preparation method of a monoatomic material described in this application includes the following steps:
(1)将前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为10 -2～10 2mbar； (1) Put the precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 10 -2 ～10 2 mbar;
(2)以5sccm～1000sccm流速通入气体1min～60min；(2) Inject gas at a flow rate of 5sccm～1000sccm for 1min～60min;
(3)采用频率为10kHz～200kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为-100℃～1500℃，处理时间为40s～240s，得到单原子材料。(3) The plasma is excited by an AC power source with a frequency of 10 kHz to 200 kHz, the precursor is treated by plasma, and the reaction temperature is controlled to be -100° C. to 1500° C., and the processing time is 40 s to 240 s to obtain monoatomic materials.
本申请的目的之二在于提供一种单原子材料，所述单原子材料通过目的之一所述制备方法得到。The second objective of this application is to provide a monoatomic material, which is obtained by the preparation method described in one of the objectives.
可选地，所述单原子材料中元素种类≥1，可选为1～10，可选为1～5，可选为1～3，例如2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20等。Optionally, the element type in the monoatomic material is ≥1, may be 1-10, may be 1-5, and may be 1-3, such as 2, 3, 4, 5, 6, 7, 8 , 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 etc.
本申请的制备方法可以实现单一元素的单原子和多种元素的单原子制备。The preparation method of the present application can realize the preparation of a single atom of a single element and a single atom of multiple elements.
可选地，所述单原子材料包括负载型和/或晶格嵌入型。Optionally, the monoatomic material includes a supported type and/or a lattice embedded type.
本申请所述负载型单原子材料为金属单原子负载在载体之上；本申请所述晶格嵌入型单原子材料为金属单原子嵌入在载体内。The supported monoatomic material of the present application is a metal single atom supported on a carrier; the lattice embedded monoatomic material of the present application is a metal single atom embedded in the carrier.
本申请的目的之三在于提供一种如目的之二所述单原子材料的用途，所述 单原子材料用于析氢电催化剂、光探测器和电子器件中的任意一种或至少两种的组合。The third object of the application is to provide a use of the monoatomic material as described in the second object, which is used for any one or a combination of at least two of the hydrogen evolution electrocatalyst, photodetector and electronic device .
本申请的目的之四在于提供一种析氢电催化剂，所述析氢电催化剂包括目的之二所述的单原子材料。The fourth object of the present application is to provide a hydrogen evolution electrocatalyst, which includes the monoatomic material described in the second object.
本申请制得的析氢电催化剂能够同时适用于催化酸性和碱性电解水析氢，产氢时电流密度可达到2A/cm 2，从而能够更好地适应工业水平的大电流密度电解水产氢。 The hydrogen evolution electrocatalyst prepared in this application can be used to catalyze the hydrogen evolution of acidic and alkaline electrolysis of water at the same time, and the current density during hydrogen production can reach 2A/cm 2 , so that it can better adapt to the industrial level of high current density electrolysis of water to produce hydrogen.
可选地，所述析氢电催化剂催化酸性电解水析氢，产氢电流密度为0.001A/cm 2～2A/cm 2，例如0.01A/cm 2、0.05A/cm 2、0.1A/cm 2、0.2A/cm 2、0.3A/cm 2、0.4A/cm 2、0.5A/cm 2、0.6A/cm 2、0.7A/cm 2、0.8A/cm 2或0.9A/cm 2等。 Optionally, the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of acidic electrolyzed water, and the hydrogen production current density is 0.001A/cm 2 ～2A/cm 2 , for example, 0.01A/cm 2 , 0.05A/cm 2 , 0.1A/cm 2 , 0.2A/cm 2 , 0.3A/cm 2 , 0.4A/cm 2 , 0.5A/cm 2 , 0.6A/cm 2 , 0.7A/cm 2 , 0.8A/cm 2 or 0.9A/cm 2, etc.
可选地，所述析氢电催化剂催化酸性电解水析氢，采用的酸性溶液为0.5～1mol/L硫酸，所述析氢电催化剂产氢电流密度为0.001A/cm 2～0.4A/cm 2，过电位为200mV～270mV；所述硫酸浓度为0.6mol/L、0.7mol/L、0.8mol/L或0.9mol/L等；所述产氢电流密度例如0.01A/cm 2、0.05A/cm 2、0.1A/cm 2、0.15A/cm 2、0.2A/cm 2、0.25A/cm 2、0.3A/cm 2或0.35A/cm 2等；所述过电位例如210mV、220mV、230mV、240mV、250mV或260mV等。 Optionally, the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of acidic electrolyzed water, the acidic solution used is 0.5-1 mol/L sulfuric acid, and the hydrogen evolution electrocatalyst has a hydrogen production current density of 0.001 A/cm 2 to 0.4 A/cm 2 . The potential is 200mV～270mV; the sulfuric acid concentration is 0.6mol/L, 0.7mol/L, 0.8mol/L or 0.9mol/L, etc.; the hydrogen production current density is, for example, 0.01A/cm 2 , 0.05A/cm 2 , 0.1A/cm 2 , 0.15A/cm 2 , 0.2A/cm 2 , 0.25A/cm 2 , 0.3A/cm 2 or 0.35A/cm 2, etc.; the overpotential is for example 210mV, 220mV, 230mV, 240mV , 250mV or 260mV, etc.
可选地，所述析氢电催化剂催化碱性电解水析氢，产氢电流密度为0.001A/cm 2～2A/cm 2，例如0.01A/cm 2、0.05A/cm 2、0.1A/cm 2、0.2A/cm 2、0.3A/cm 2、0.4A/cm 2、0.5A/cm 2、0.6A/cm 2、0.7A/cm 2、0.8A/cm 2或0.9A/cm 2等。 Optionally, the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of alkaline water electrolysis, and the hydrogen production current density is 0.001A/cm 2 ～2A/cm 2 , for example, 0.01A/cm 2 , 0.05A/cm 2 , 0.1A/cm 2 , 0.2A/cm 2 , 0.3A/cm 2 , 0.4A/cm 2 , 0.5A/cm 2 , 0.6A/cm 2 , 0.7A/cm 2 , 0.8A/cm 2 or 0.9A/cm 2, etc.
可选地，所述析氢电催化剂催化碱性电解水析氢，采用的碱性溶液包括氢氧化钾和/或氢氧化钠。Optionally, the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of alkaline electrolyzed water, and the adopted alkaline solution includes potassium hydroxide and/or sodium hydroxide.
可选地，所述碱性溶液为0.5～1mol/L氢氧化钾水溶液，产氢电流密度为 0.001A/cm 2～0.4A/cm 2，过电位为200mV～300mV。所述碱性溶液浓度为0.6mol/L、0.7mol/L、0.8mol/L或0.9mol/L等；所述产氢电流密度例如0.01A/cm 2、0.05A/cm 2、0.1A/cm 2、0.15A/cm 2、0.2A/cm 2、0.25A/cm 2、0.3A/cm 2或0.35A/cm 2等；所述过电位例如210mV、220mV、230mV、240mV、250mV、260mV、270mV、280mV或290mV等。 Optionally, the alkaline solution is 0.5 to 1 mol/L potassium hydroxide aqueous solution, the hydrogen production current density is 0.001 A/cm 2 to 0.4 A/cm 2 , and the overpotential is 200 mV to 300 mV. The concentration of the alkaline solution is 0.6 mol/L, 0.7 mol/L, 0.8 mol/L or 0.9 mol/L, etc.; the hydrogen production current density is, for example, 0.01 A/cm 2 , 0.05 A/cm 2 , 0.1 A/ cm 2 , 0.15A/cm 2 , 0.2A/cm 2 , 0.25A/cm 2 , 0.3A/cm 2 or 0.35A/cm 2, etc.; the overpotential is for example 210mV, 220mV, 230mV, 240mV, 250mV, 260mV , 270mV, 280mV or 290mV, etc.
与现有技术相比，本申请具有如下有益结果：Compared with the prior art, this application has the following beneficial results:
(1)本申请创造性地提出采用等离子体制备含金属元素的单原子材料，适用于不同形式的负载基底，对不同金属元素也具有普适性，本申请的方法可适用于所有金属元素的单原子材料制备，特别是可用于实现两种及以上不同金属元素单原子材料的制备，另外，该方法具有快速、简单的优势。(1) This application creatively proposes the use of plasma to prepare metal element-containing monoatomic materials, which is suitable for different forms of load substrates and has universal applicability to different metal elements. The method of this application can be applied to all metal elements. The preparation of atomic materials is particularly applicable to the preparation of two or more different metal element monoatomic materials. In addition, the method has the advantages of rapidness and simplicity.
(2)本申请通过控制通入的反应气氛的气体种类和流量、反应时间和温度，实现一系列单原子材料的可控制备。(2) This application realizes the controllable preparation of a series of monoatomic materials by controlling the gas type and flow rate, reaction time and temperature of the introduced reaction atmosphere.
(3)本申请制得的析氢电催化剂能够同时适用于催化酸性和碱性电解水析氢，产氢时电流密度可达到2A/cm 2，从而能够更好地适应工业水平的大电流密度电解水产氢。 (3) The hydrogen evolution electrocatalyst prepared in this application can be used to catalyze the hydrogen evolution of acidic and alkaline electrolysis of water at the same time, and the current density during hydrogen production can reach 2A/cm 2 , so as to better adapt to the industrial level of high current density electrolysis of aquatic products hydrogen.
附图说明Description of the drawings
图1为本申请利用等离子体技术制备单原子材料的方法示意图；FIG. 1 is a schematic diagram of a method for preparing monoatomic materials using plasma technology in this application;
图2为本申请实施例1制备的钼单原子材料的透射电镜图；2 is a transmission electron microscope image of the molybdenum monoatomic material prepared in Example 1 of this application;
图3为本申请实施例1制备的类型一钼单原子材料的透射电镜图；FIG. 3 is a transmission electron microscope image of a type-molybdenum monoatomic material prepared in Example 1 of this application;
图4为本申请实施例1制备的类型一钼单原子材料的模拟图；Fig. 4 is a simulation diagram of a type-molybdenum monoatomic material prepared in Example 1 of this application;
图5为本申请实施例1制备的类型一钼单原子的强度刨面图；Fig. 5 is a plan view of the intensity of a single molybdenum atom of type 1 prepared in Example 1 of the application;
图6为本申请实施例1制备的类型二钼单原子材料的透射电镜图；Fig. 6 is a transmission electron microscope image of the type di-molybdenum monoatomic material prepared in Example 1 of the application;
图7为本申请实施例1制备的类型二钼单原子材料的模拟图；Fig. 7 is a simulation diagram of the type di-molybdenum monoatomic material prepared in Example 1 of the application;
图8为本申请实施例1制备的类型二钼单原子的强度刨面图；Fig. 8 is a plan view of the strength of the type di-molybdenum single atom prepared in Example 1 of the application;
图9为本申请实施例4制备的钨单原子材料的透射电镜图；9 is a transmission electron microscope image of the tungsten monoatomic material prepared in Example 4 of this application;
图10为本申请实施例4制备的类型一和类型二的钨单原子材料的透射电镜图；10 is a transmission electron microscope image of Type 1 and Type 2 tungsten monoatomic materials prepared in Example 4 of this application;
图11为本申请实施例4制备的类型一和类型二的钨单原子材料的模拟图；11 is a simulation diagram of Type 1 and Type 2 tungsten single-atom materials prepared in Example 4 of this application;
图12为本申请实施例4制备的类型一钨单原子的强度刨面图；12 is a plan view of the strength of a single tungsten atom of type one prepared in Example 4 of this application;
图13为本申请实施例4制备的类型二钨单原子的强度刨面图；13 is a plan view of the strength of a single atom of type two tungsten prepared in Example 4 of the application;
图14为本申请实施例1制备的单原子材料在0.5mol/L硫酸水溶液中析氢反应的电流密度-过电势曲线图；Fig. 14 is a current density-overpotential curve diagram of the hydrogen evolution reaction of the monoatomic material prepared in Example 1 of the application in a 0.5 mol/L sulfuric acid aqueous solution;
图15为本申请实施例1制备的单原子材料在1.0mol/L的氢氧化钾水溶液中析氢反应的电流密度-过电势曲线图。FIG. 15 is a current density-overpotential curve diagram of the hydrogen evolution reaction of the monoatomic material prepared in Example 1 of the application in a 1.0 mol/L potassium hydroxide aqueous solution.
具体实施方式Detailed ways
为便于理解本申请，本申请列举实施例如下，本申请实施例中等离子体技术制备单原子材料的方法示意图如图1所示，图中前驱体即为本申请所述前驱物。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。In order to facilitate the understanding of this application, the following examples are listed in this application. The schematic diagram of the method for preparing monoatomic materials by plasma technology in the examples of this application is shown in FIG. 1, and the precursor in the figure is the precursor described in this application. It should be understood by those skilled in the art that the described embodiments are only to help understand the application and should not be regarded as specific limitations to the application.
实施例1Example 1
一种单原子材料的制备方法包括如下步骤：A preparation method of monoatomic material includes the following steps:
(1)将单原子层二硫化钼前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为1.5mbar；(1) Place the monoatomic molybdenum disulfide precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 1.5 mbar;
(2)以20sccm流速通入氢气2min至气压稳定；(2) Feed hydrogen gas at a flow rate of 20 sccm for 2 minutes until the pressure is stable;
(3)采用频率为100kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为60℃，处理时间为80s，得到钼单原子材料。(3) Using an AC power source with a frequency of 100kHz to excite the plasma, using the plasma to process the precursor, controlling the reaction temperature to 60°C, and the processing time to 80s, to obtain a molybdenum monatomic material.
图2为所述钼单原子材料的原子分辨的透射电镜图，图3和图4分别为类型一的钼单原子材料的透射电镜图及其模拟图，由图中可以看出制得的钼单原子的载量高、分布均匀；图5为类型一的钼单原子的强度刨面图；类型二的钼单原子透射电镜图及其模拟图分别如图6和图7所示，图8为类型二钼单原子的强度刨面图，综合图2-8可以看出，制备得到的单原子材料为负载在二硫化钼前驱物上的钼单原子材料。Figure 2 is an atomically resolved transmission electron microscope image of the molybdenum monoatomic material. Figures 3 and 4 are respectively a transmission electron microscope image of the molybdenum monoatomic material of type one and its simulation diagram. It can be seen from the figure that the obtained molybdenum The single-atom load is high and the distribution is uniform; Figure 5 is a plan view of the intensity of a single molybdenum atom of type one; the transmission electron microscope image of a single-atom molybdenum atom of type two and its simulation are shown in Figure 6 and Figure 7, respectively, and Figure 8 It is a plan view of the strength of a type of molybdenum monoatom. It can be seen from Figures 2-8 that the prepared monoatomic material is a molybdenum monoatomic material supported on a molybdenum disulfide precursor.
将本实施例得到的钼单原子材料作为催化剂进行电解水析氢反应，所述钼单原子材料分别在0.5mol/L的硫酸水溶液和1.0mol/L的氢氧化钾水溶液中析氢反应的电流密度-过电势曲线分别如图14和图15所示，图中钼单原子/二硫化钼复合体系即为本实施例中钼单原子负载在二硫化钼前驱物上作为催化剂，图中铂为商用铂催化剂，二硫化钼为商用二硫化钼催化剂，由图14和图15可以看出，所得单原子材料作为析氢电催化剂应用于酸性或碱性溶液均具有较好活性。The molybdenum monoatomic material obtained in this example was used as a catalyst for the hydrogen evolution reaction of electrolyzed water. The current density of the molybdenum monoatomic material in the 0.5mol/L sulfuric acid aqueous solution and 1.0mol/L potassium hydroxide aqueous solution respectively The overpotential curves are shown in Figure 14 and Figure 15, respectively. The molybdenum single atom/molybdenum disulfide composite system in the figure is the molybdenum single atom supported on the molybdenum disulfide precursor as a catalyst in this example. The platinum in the figure is commercial platinum The catalyst, molybdenum disulfide is a commercial molybdenum disulfide catalyst. It can be seen from Figure 14 and Figure 15 that the obtained monoatomic material has good activity when used as an electrocatalyst for hydrogen evolution in acidic or alkaline solutions.
实施例2Example 2
与实施例1的区别在于，步骤(3)等离子体处理时间为160s。The difference from Embodiment 1 is that the plasma treatment time in step (3) is 160s.
实施例3Example 3
与实施例1的区别在于，步骤(3)采用频率为20kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为200℃，处理时间为240s，得到钼单原子材料。The difference from Example 1 is that in step (3), an AC power source with a frequency of 20 kHz is used to excite the plasma, the precursor is treated with plasma, the reaction temperature is controlled to 200° C., and the treatment time is 240 s to obtain a molybdenum monoatomic material.
实施例4Example 4
与实施例1的区别在于，步骤(1)中单原子层二硫化钼前驱物替换为单原 子层二硫化钨前驱物，得到钨单原子材料。The difference from Example 1 is that in step (1), the monoatomic layer molybdenum disulfide precursor is replaced with a monoatomic layer tungsten disulfide precursor to obtain a tungsten monoatomic material.
图9为所述钨单原子材料的原子分辨的透射电镜图，由图中可以看出制得的钨单原子的载量高、分布均匀；图10和图11分别为类型一(图中为钨单原子1)和类型二(图中为钨单原子2)的钨单原子透射电镜图及其模拟图；图12和图13分别为类型一(图中为钨单原子1)和类型二(图中为钨单原子2)的钨单原子强度刨面图；综合图9-13可以看出，制备得到的单原子材料为负载在二硫化钨前驱物上的钨单原子材料，且负载的位置有类型一和类型二两种。Figure 9 is an atomically resolved transmission electron microscope image of the tungsten single-atom material. It can be seen from the figure that the prepared tungsten single-atom has a high loading and uniform distribution; Figures 10 and 11 are type one (the figure is Tungsten single atom 1) and type 2 (tungsten single atom 2 in the figure) of tungsten single atom transmission electron microscope images and their simulation images; Figures 12 and 13 are type 1 (tungsten single atom 1 in the figure) and type 2 respectively (The figure shows the tungsten single atom 2) the plan view of the tungsten single-atom strength; comprehensively shown in Figures 9-13, the prepared single-atom material is a tungsten single-atom material supported on a tungsten disulfide precursor, and There are two types of location: Type One and Type Two.
实施例5Example 5
一种单原子材料的制备方法包括如下步骤：A preparation method of monoatomic material includes the following steps:
(1)将氧化铋前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为10 -5mbar； (1) Put the bismuth oxide precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 10 -5 mbar;
(2)以40sccm流速通入甲烷和20sccm氢气5min至气压稳定；(2) Feed methane and 20sccm hydrogen at a flow rate of 40sccm for 5min until the pressure is stable;
(3)采用频率为10kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为150℃，处理时间为20min，得到铋单原子材料。(3) Using an AC power source with a frequency of 10kHz to excite the plasma, using the plasma to process the precursor, controlling the reaction temperature to 150°C, and the processing time to 20min, to obtain a bismuth monoatomic material.
实施例6Example 6
一种单原子材料的制备方法包括如下步骤：A preparation method of monoatomic material includes the following steps:
(1)将二硫化钼前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为10 -5mbar； (1) Put the molybdenum disulfide precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 10 -5 mbar;
(2)以40sccm流速通入氨气和20sscm氢气5min至气压稳定；(2) Feed ammonia and 20sscm hydrogen at a flow rate of 40sccm for 5 minutes until the pressure is stable;
(3)采用频率为22kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为50℃，处理时间为240s，得到钼单原子材料。(3) The plasma is excited by an AC power source with a frequency of 22 kHz, the precursor is treated by plasma, the reaction temperature is controlled to 50° C., and the treatment time is 240 s to obtain a molybdenum monoatomic material.
实施例7Example 7
一种单原子材料的制备方法包括如下步骤：A preparation method of monoatomic material includes the following steps:
(1)将二硫化钼前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为10 -2mbar； (1) Put the molybdenum disulfide precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 10 -2 mbar;
(2)以20sccm的速度通入氢气和40sccm流速通入氨气，维持5min至气压稳定；(2) Feed hydrogen gas at a rate of 20 sccm and ammonia gas at a flow rate of 40 sccm, and maintain for 5 minutes until the pressure is stable;
(3)采用频率为22kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为50℃，处理时间为240s，得到钼单原子材料。(3) Using an AC power source with a frequency of 22kHz to excite the plasma, using the plasma to process the precursor, controlling the reaction temperature to 50°C, and the processing time to 240s, to obtain a molybdenum monoatomic material.
实施例8Example 8
一种单原子材料的制备方法包括如下步骤：A preparation method of monoatomic material includes the following steps:
(1)将磷化铁前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为10 -9mbar； (1) Put the iron phosphide precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 10 -9 mbar;
(2)以80sccm的速度通入氢气，维持5min至气压稳定；(2) Feed hydrogen gas at a rate of 80 sccm and maintain it for 5 minutes until the pressure is stable;
(3)采用频率为10kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为100℃，处理时间为40s，得到钼单原子材料。(3) Using an AC power source with a frequency of 10kHz to excite the plasma, using the plasma to process the precursor, controlling the reaction temperature to 100°C, and the processing time to 40s, to obtain a molybdenum monatomic material.
实施例9Example 9
(1)将二硫化钒-钼合金(V 0.1Mo 0.9S 2)前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为1.5mbar； (1) Put the vanadium disulfide-molybdenum alloy (V 0.1 Mo 0.9 S 2 ) precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 1.5 mbar;
(2)以40sccm流速通入氢气2min至气压稳定；(2) Feed hydrogen gas at a flow rate of 40 sccm for 2 minutes until the pressure is stable;
(3)采用频率为100kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为100℃，处理时间为160s，得到钼、钒两种元素的单原子材料，即钼单原子和钒单原子。(3) The plasma is excited by an AC power source with a frequency of 100kHz, the precursor is treated by plasma, the reaction temperature is controlled at 100°C, and the treatment time is 160s, to obtain a monoatomic material of molybdenum and vanadium, namely molybdenum monoatom and Vanadium single atom.
实施例10Example 10
(1)将二硫化铌-钨合金(Nb 0.1W 0.9S 2)前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为1.5mbar； (1) Put the niobium disulfide-tungsten alloy (Nb 0.1 W 0.9 S 2 ) precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 1.5 mbar;
(2)以40sccm流速通入氢气2min至气压稳定；(2) Feed hydrogen gas at a flow rate of 40 sccm for 2 minutes until the pressure is stable;
(3)采用频率为22kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为120℃，处理时间为80s，得到钨、铌两种元素的单原子材料，即钨单原子和铌单原子。(3) The plasma is excited by an AC power source with a frequency of 22kHz, and the precursor is treated by plasma. The reaction temperature is controlled to 120°C and the treatment time is 80s to obtain monoatomic materials of tungsten and niobium. Niobium single atom.
实施例11Example 11
一种单原子材料的制备方法包括如下步骤：A preparation method of monoatomic material includes the following steps:
(1)将硒化铟前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为10 0mbar； (1) The indium selenide precursor in the reaction chamber, the reaction chamber is evacuated to a vacuum of the reaction chamber is 10 0 mbar;
(2)以100sccm流速通入氩气1min至气压稳定；(2) Pour argon gas at a flow rate of 100 sccm for 1 min until the pressure is stable;
(3)采用频率为100MHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为700℃，处理时间为10h，得到铟单原子材料。(3) Using an AC power source with a frequency of 100 MHz to excite the plasma, using the plasma to process the precursor, controlling the reaction temperature to 700° C., and the processing time for 10 hours to obtain an indium monoatomic material.
实施例12Example 12
一种单原子材料的制备方法包括如下步骤：A preparation method of monoatomic material includes the following steps:
(1)将硫化铂前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为10 -9mbar； (1) Put the platinum sulfide precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 10 -9 mbar;
(2)以5sccm流速通入氩气60min至气压稳定；(2) Pour argon gas at a flow rate of 5 sccm for 60 minutes until the pressure is stable;
(3)采用频率为5000Hz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为20℃，处理时间为2s，得到铂单原子材料。(3) Using an AC power source with a frequency of 5000 Hz to excite the plasma, using the plasma to process the precursor, controlling the reaction temperature to 20° C., and the processing time to 2 s to obtain platinum monoatomic materials.
性能测试：Performance Testing:
将得到的单原子材料进行如下性能测试：Perform the following performance tests on the obtained monoatomic material:
(1)载量：用高分辨透射电子显微镜表征单原子的载量，
Figure PCTCN2019091353-appb-000001
(1) Carrying capacity: Use high resolution transmission electron microscope to characterize the carrying capacity of single atoms,
Figure PCTCN2019091353-appb-000001
表1Table 1
 To 载量(wt％)Load (wt%)
实施例1Example 1 22
实施例2Example 2 55
实施例3Example 3 11
实施例4Example 4 22
实施例5Example 5 44
实施例6Example 6 22
实施例7Example 7 22
实施例8Example 8 44
实施例9Example 9 33
实施例10Example 10 55
实施例11Example 11 55
实施例12Example 12 44
通过表1可以看出，本申请得到的单原子材料载量较高，为1～5wt％，并且可以实现两种及以上不同金属元素单原子材料的制备。It can be seen from Table 1 that the monoatomic material obtained in this application has a relatively high loading of 1 to 5 wt%, and the preparation of two or more different metal element monoatomic materials can be achieved.
申请人声明，本申请通过上述实施例来说明本申请的详细工艺设备和工艺流程，但本申请并不局限于上述详细工艺设备和工艺流程，即不意味着本申请必须依赖上述详细工艺设备和工艺流程才能实施。The applicant declares that this application uses the above embodiments to illustrate the detailed process equipment and process flow of this application, but this application is not limited to the above detailed process equipment and process flow, which does not mean that this application must rely on the above detailed process equipment and The process can be implemented.

Claims (12)

  1. 一种单原子材料的制备方法，其中，所述方法包括如下步骤：A method for preparing monoatomic materials, wherein the method includes the following steps:
    采用等离子体处理前驱物，得到单原子材料，所述单原子材料中的元素包含金属元素。The precursor is processed by plasma to obtain a monoatomic material, and the elements in the monoatomic material include metal elements.
  2. 如权利要求1所述的制备方法，其中，所述前驱物包括金属氧化物、金属硫族化合物、金属磷化物、金属卤化物和金属碳化物中的任意一种或至少两种的组合；The preparation method according to claim 1, wherein the precursor comprises any one or a combination of at least two of metal oxides, metal chalcogenides, metal phosphides, metal halides and metal carbides;
    可选地，所述前驱物中的金属元素包括钼、钨、铂、铟、铁、铌、金、钴、镍、锰、铬和铋中的任意一种或至少两种的组合；Optionally, the metal element in the precursor includes any one or a combination of at least two of molybdenum, tungsten, platinum, indium, iron, niobium, gold, cobalt, nickel, manganese, chromium and bismuth;
    可选地，所述前驱物的形貌包括块体材料、粉末材料、薄膜材料和介孔材料中的任意一种或至少两种的组合。Optionally, the morphology of the precursor includes any one or a combination of at least two of bulk material, powder material, thin film material and mesoporous material.
  3. 如权利要求1或2所述的制备方法，其中，所述等离子体处理前驱物的过程中，反应腔室的真空度为10 -9mbar～10 2mbar，可选为10 -2～10 2mbar； The preparation method according to claim 1 or 2, wherein, during the plasma treatment of the precursor, the vacuum degree of the reaction chamber is 10 -9 mbar to 10 2 mbar, optionally 10 -2 to 10 2 mbar;
    可选地，所述等离子体处理前驱物的过程中，反应温度为-100℃～1500℃；Optionally, during the plasma treatment of the precursor, the reaction temperature is -100°C to 1500°C;
    可选地，所述前驱物中的金属元素包括钼和/或钨，所述反应温度≤200℃；Optionally, the metal element in the precursor includes molybdenum and/or tungsten, and the reaction temperature is ≤200°C;
    可选地，所述前驱物中的金属元素包括铁和/或铋，所述反应温度≤150℃；Optionally, the metal element in the precursor includes iron and/or bismuth, and the reaction temperature is ≤150°C;
    可选地，所述等离子体处理前驱物的过程中，反应时间为2s～20h，可选为5s～60min，可选为40s～240s。Optionally, during the plasma treatment of the precursor, the reaction time is 2 s to 20 h, optionally 5 s to 60 min, and optionally 40 s to 240 s.
  4. 权利要求1-3之一所述的制备方法，其中，所述等离子体的制备过程包括：激发气体，生成等离子体；The preparation method according to any one of claims 1 to 3, wherein the preparation process of the plasma comprises: exciting gas to generate plasma;
    可选地，所述等离子体制备过程中，反应腔室的真空度为10 -9mbar～10 2mbar，可选为10 -2～10 2mbar； Optionally, during the plasma preparation process, the vacuum degree of the reaction chamber is 10 -9 mbar to 10 2 mbar, and may be 10 -2 to 10 2 mbar;
    可选地，所述等离子体制备过程中，采用的气体包括空气、氧气、氢气、 氩气、甲烷、氮气和氨气中的任意一种或至少两种的组合；Optionally, in the plasma preparation process, the gas used includes any one or a combination of at least two of air, oxygen, hydrogen, argon, methane, nitrogen, and ammonia;
    可选地，所述等离子体的制备过程中，通入气体流速为5sccm～1000sccm；Optionally, during the preparation of the plasma, the flow rate of the introduced gas is 5 sccm to 1000 sccm;
    可选地，所述通入气体的时间为1min～60min；Optionally, the time for introducing the gas is 1 min to 60 min;
    可选地，所述激发等离子体采用的交流电源频率为50Hz～100MHz，可选为10kHz～200kHz；Optionally, the AC power frequency used to excite the plasma is 50 Hz-100 MHz, and may be 10 kHz-200 kHz;
    可选地，所述激发等离子体采用的直流放电电压为1V～1000V。Optionally, the DC discharge voltage used to excite the plasma is 1V˜1000V.
  5. 权利要求1-4之一所述的制备方法，其中，所述制备方法包括如下步骤：The preparation method of any one of claims 1-4, wherein the preparation method comprises the following steps:
    (1)将前驱物放在反应室内，将反应室抽真空至反应腔室的真空度为10 -2～10 2mbar； (1) Put the precursor in the reaction chamber, and evacuate the reaction chamber until the vacuum degree of the reaction chamber is 10 -2 ～10 2 mbar;
    (2)以5sccm～1000sccm流速通入气体1min～60min；(2) Inject gas at a flow rate of 5sccm～1000sccm for 1min～60min;
    (3)采用频率为10kHz～200kHz的交流电源激发等离子体，采用等离子体处理前驱物，控制反应温度为-100℃～1500℃，处理时间为40s～240s，得到单原子材料。(3) The plasma is excited by an AC power source with a frequency of 10 kHz to 200 kHz, the precursor is treated by plasma, and the reaction temperature is controlled to be -100° C. to 1500° C., and the processing time is 40 s to 240 s to obtain monoatomic materials.
  6. 一种单原子材料，其中，所述单原子材料通过权利要求1～5之一所述制备方法得到。A monoatomic material, wherein the monoatomic material is obtained by the preparation method of any one of claims 1 to 5.
  7. 如权利要求6所述的单原子材料，其中，所述单原子材料中元素种类≥1，可选为1～10，可选为1～5，可选为1～3。7. The monoatomic material of claim 6, wherein the element type in the monoatomic material is ≥1, optionally 1-10, optionally 1-5, and optionally 1-3.
  8. 如权利要求6或7所述的单原子材料，其中，所述单原子材料包括负载型和/或晶格嵌入型。The monoatomic material according to claim 6 or 7, wherein the monoatomic material includes a supported type and/or a lattice embedded type.
  9. 一种如权利要求6-8任一项所述单原子材料的用途，其中，所述单原子材料用于析氢电催化剂、光探测器和电子器件中的任意一种或至少两种的组合。A use of the monoatomic material according to any one of claims 6-8, wherein the monoatomic material is used for any one or a combination of at least two of hydrogen evolution electrocatalysts, photodetectors and electronic devices.
  10. 一种析氢电催化剂，其中，所述析氢电催化剂包括权利要求6-8任一项 所述的单原子材料。A hydrogen evolution electrocatalyst, wherein the hydrogen evolution electrocatalyst comprises the monoatomic material according to any one of claims 6-8.
  11. 如权利要求10所述的析氢电催化剂，其中，所述析氢电催化剂催化酸性电解水析氢，产氢电流密度为0.001A/cm 2～2A/cm 2； 10. The hydrogen evolution electrocatalyst according to claim 10, wherein the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of acidic electrolyzed water, and the hydrogen production current density is 0.001 A/cm 2 -2A/cm 2 ;
    可选地，所述析氢电催化剂催化酸性电解水析氢，采用的酸性溶液为0.5～1mol/L硫酸，所述析氢电催化剂产氢电流密度为0.001A/cm 2～0.4A/cm 2，过电位为200mV～270mV。 Optionally, the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of acidic electrolyzed water, the acidic solution used is 0.5-1 mol/L sulfuric acid, and the hydrogen evolution electrocatalyst has a hydrogen production current density of 0.001 A/cm 2 to 0.4 A/cm 2 . The potential is 200mV～270mV.
  12. 如权利要求10所述的析氢电催化剂，其中，所述析氢电催化剂催化碱性电解水析氢，产氢电流密度为0.001A/cm 2～2A/cm 2； 10. The hydrogen evolution electrocatalyst according to claim 10, wherein the hydrogen evolution electrocatalyst catalyzes the hydrogen evolution of alkaline water electrolysis, and the hydrogen production current density is 0.001 A/cm 2 ～2A/cm 2 ;
    可选地，所述析氢电催化剂催化碱性电解水析氢，采用的碱性溶液包括氢氧化钾和/或氢氧化钠；Optionally, the hydrogen evolution electrocatalyst catalyzes the alkaline electrolysis of water for hydrogen evolution, and the used alkaline solution includes potassium hydroxide and/or sodium hydroxide;
    可选地，所述碱性溶液为0.5～1mol/L氢氧化钾水溶液，产氢电流密度为0.001A/cm 2～0.4A/cm 2，过电位为200mV～300mV。 Optionally, the alkaline solution is 0.5 to 1 mol/L potassium hydroxide aqueous solution, the hydrogen production current density is 0.001 A/cm 2 to 0.4 A/cm 2 , and the overpotential is 200 mV to 300 mV.
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