WO2018019234A1 - 一种MoSxOy/碳纳米复合材料、其制备方法及其应用 - Google Patents

一种MoSxOy/碳纳米复合材料、其制备方法及其应用 Download PDF

Info

Publication number
WO2018019234A1
WO2018019234A1 PCT/CN2017/094333 CN2017094333W WO2018019234A1 WO 2018019234 A1 WO2018019234 A1 WO 2018019234A1 CN 2017094333 W CN2017094333 W CN 2017094333W WO 2018019234 A1 WO2018019234 A1 WO 2018019234A1
Authority
WO
WIPO (PCT)
Prior art keywords
mos
carbon
electrode
source
nanocomposite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/094333
Other languages
English (en)
French (fr)
Inventor
翟茂林
曹朋飞
彭静
李久强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Peking University
Original Assignee
Peking University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Peking University filed Critical Peking University
Priority to US16/320,450 priority Critical patent/US11349116B2/en
Priority to JP2019503982A priority patent/JP6814996B2/ja
Priority to EP17833537.8A priority patent/EP3511297B1/en
Publication of WO2018019234A1 publication Critical patent/WO2018019234A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • 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
    • Y02E60/50—Fuel cells

Definitions

  • the present application relates to the field of composite materials, and in particular to a MoS x O y /carbon nanocomposite, a preparation method thereof and application thereof.
  • Hydrogen as a clean new energy source has great significance for environmental protection and energy security. How to prepare hydrogen on a large scale is a fundamental problem in the commercial use of hydrogen energy.
  • the Hydrogen Evolution Reaction (HER) is considered as a feasible solution for the large-scale preparation of hydrogen, but the reaction has a high cathode overpotential on the cathode, resulting in a significant increase in the energy cost of preparing hydrogen.
  • HER Hydrogen Evolution Reaction
  • platinum-based noble metals can well reduce the cathode overpotential, but due to the limited reserves of platinum-based precious metals on the earth, they cannot meet the needs of large-scale applications. Therefore, finding alternative catalytic materials, reducing cathode overpotentials and reducing production costs has become a focus of researchers' attention.
  • Molybdenum disulfide (MoS 2 ) is a layered structural compound having a graphite-like structure.
  • Molybdenum disulfide block When the molybdenum disulfide block is used as a catalyst for HER, it has a high overpotential, and when the number of layers is reduced to the oligo layer or even the monolayer, the physicochemical properties of the block will change significantly.
  • the layer of molybdenum disulfide material has good HER catalytic activity (Berit H., Poul GM, Bonde, KP J. Nielsen, S. Chorkendorff, JK Journal of the American Chemistry Society 2005, 127, 5308-5309).
  • the purpose of the present application is to provide a MoS x O y /carbon nanocomposite which has better catalytic performance for electrochemical hydrogen evolution reaction than the existing MoS 2 composite material (Mo stands for molybdenum element, S stands for sulfur element, and O stands for oxygen element) And its preparation method and its application (in the present application, MoS x O y is also referred to as oxygen-doped molybdenum sulfide).
  • Mo molybdenum element
  • S sulfur element
  • O oxygen element
  • the present application first provides a MoS x O y /carbon nanocomposite wherein 2.5 ⁇ x ⁇ 3.1 and 0.2 ⁇ y ⁇ 0.7.
  • the mass percentage of the MoS x O y is 5-50% based on the total mass of the nanocomposite.
  • the MoS x O y is an amorphous structure.
  • the present application also provides the foregoing method for preparing a nanocomposite, wherein the method comprises the following steps:
  • a carbon source is preferably selected from carbon black, carbon nanotubes, carbon nanohorns, graphite oxide, sulfonation At least one of graphite oxide;
  • the solvent is preferably selected from at least one of ethylene glycol, glycerol, and water;
  • the sulfur source and the molybdenum source are the same compound, and the concentration of the compound in the mixed solution is 1-10 mg/mL, preferably 1-5 mg/mL, and the compound is preferably selected from the group consisting of At least one of ammonium tetrathiomolybdate and sodium tetrathiomolybdate.
  • the sulfur source and the molybdenum source are different compounds, and the concentration of the molybdenum source and the sulfur source in the mixed solution is 2-10 mg/mL, and the total molar amount of the molybdenum atoms in the molybdenum source.
  • the ratio of the number to the total number of moles of sulfur atoms in the sulfur source is from 1:2 to 1:6.
  • the sulfur source is at least one selected from the group consisting of thiourea and sodium thiosulfate; and the molybdenum source is selected from the group consisting of ammonium molybdate, molybdenum pentachloride, and sodium molybdate. At least one.
  • the ratio of the carbon source to the solvent is 1-10 mg: 1 mL.
  • the absorbed dose rate when the mixed solution is irradiated is 30-30000 Gy/min (minute), and the absorbed dose may be 20000-400000 Gy.
  • the gamma ray is 60 Co gamma ray; the electron beam is generated by an electron accelerator having an energy of 0.5 to 5 MeV.
  • the method before the irradiating the mixed solution in step 3), the method further includes the step of introducing an inert gas into the mixed solution, preferably the nitrogen gas, the argon gas or Their mixed gas.
  • the separated solid product is sequentially ultrasonically washed with a water-miscible alcohol and water.
  • the application also provides the aforementioned application of the MoS x O y /carbon nanocomposite in the electrochemical hydrogen evolution reaction.
  • the present application provides a cathode electrode, wherein the cathode electrode comprises a base electrode and the aforementioned MoS x O y /carbon nanocomposite coated on the surface of the base electrode, the base electrode being an inert electrode, preferably It is selected from a gold electrode, a platinum electrode, a glassy carbon electrode, a graphite electrode, an ITO electrode or an FTO electrode.
  • the present application provides an electrolyzed water hydrogen production apparatus, wherein the apparatus includes the aforementioned cathode electrode.
  • the present application provides a hydrogen fuel cell device, wherein the hydrogen fuel cell device includes a hydrogen fuel cell body and the aforementioned electrolyzed water hydrogen plant.
  • the present application provides an electric device, wherein the electric device includes the aforementioned hydrogen fuel cell device, which is preferably an electric car, an electric tricycle or an electric bicycle.
  • a highly conductive carbon material is selected as the carbon source in the composite material, and MoS x O y /carbon nanocomposites are prepared by radiation method, wherein the carbon material can enhance MoS x O y / carbon nanometer on the one hand.
  • the three-dimensional network structure of the carbon material is beneficial to the sufficient contact between the electrolyte and the nanocomposite; in addition, the generated MoS x O y is an amorphous structure, which increases the catalytic effect in the nanocomposite.
  • the O element introduced by the radiation method can improve the conductivity of the nanocomposite and further enhance the catalytic ability of the nanocomposite.
  • the catalytic performance of the MoS x O y /carbon nanocomposite prepared by the present application on the electrocatalytic hydrogen evolution reaction is superior to that of other catalysts containing molybdenum disulfide; and when the MoS x O y / carbon nanometer prepared by the present application is used
  • the current density at an overpotential of 300 mV is 150 mA/cm 2 or more, preferably 200 mA/cm 2 or more, and more preferably 300 mA/cm 2 or more. This performance is small or even comparable to the commercial 20% Pt/C catalyst performance (current density of 370 mA/cm 2 at an overpotential of 300 mV).
  • the MoS x O y /carbon nanocomposite prepared by the present application has good catalytic stability, and the current density is only 3% when the overpotential is 300 mV after 8000 catalytic cycles, which is very excellent. Catalytic performance and cycle stability.
  • the radiation preparation method has simple preparation device, mild reaction condition, simple operation, good repeatability, low energy consumption, small environmental pollution and strong applicability.
  • macro preparation it has good industrial application prospects.
  • Example 1 is a transmission electron microscope (TEM) image of a MoS x O y /carbon nanocomposite prepared in Example 1;
  • Example 2 is an X-ray diffraction (XRD) pattern of the MoS x O y /carbon nanocomposite prepared in Example 1;
  • FIG. 3 is an X-ray photoelectron spectroscopy (XPS) diagram of the MoS x O y /carbon nanocomposite prepared in Example 1; wherein FIG. 3A is an XPS high resolution diagram of Mo; and FIG. 3B is an XPS high resolution diagram of S;
  • XPS X-ray photoelectron spectroscopy
  • LSV linear sweep voltammetry test
  • Example 5 is a linear sweep voltammetry test (LSV) diagram of the MoS x O y /carbon nanocomposite prepared in Example 1 after catalytic cycling.
  • LSV linear sweep voltammetry test
  • the present application first provides a MoS x O y /carbon nanocomposite wherein 2.5 ⁇ x ⁇ 3.1, 0.2 ⁇ y ⁇ 0.7, preferably 2.6 ⁇ x ⁇ 3.1, 0.25 ⁇ y ⁇ 0.7.
  • the mass percentage of MoS x O y is from 5 to 50%, preferably from 15 to 40%, based on the total mass of the nanocomposite.
  • the MoS x O y is an amorphous structure, and the amorphous structure MoS x O y is more likely to expose more reactive catalytic active sites than the ordered crystal structure.
  • the present application also provides the foregoing method for preparing a nanocomposite, wherein the method comprises the following steps:
  • the ratio of the carbon source to the solvent is 1-10 mg: 1 mL;
  • the carbon source is preferably selected from the group consisting of carbon black, carbon nanotubes, carbon nanohorns, graphite oxide, and sulfonated graphite oxide.
  • the solvent is preferably selected from at least one of ethylene glycol, glycerol, and water, preferably deionized water; in a specific implementation, ultrasonic dispersion is more preferably 60-100 minutes; ultrasonic power may be 500. -1200W.
  • the sulfur source and the molybdenum source may be the same compound or different compounds; when the sulfur source and the molybdenum source are the same compound, the compound contains both sulfur and molybdenum.
  • Such compounds include, but are not limited to, ammonium tetrathiomolybdate or sodium tetrathiomolybdate or a combination thereof.
  • the concentration of the compound containing both sulfur and molybdenum in the mixed solution may be 1-10 mg/mL, preferably 1-5 mg/mL.
  • the sulfur source includes, but is not limited to, at least one of thiourea and sodium thiosulfate
  • the molybdenum source includes, but is not limited to, ammonium molybdate, molybdenum pentachloride, sodium molybdate.
  • At least one of the molybdenum source and the sulfur source in the mixed solution is 2-10 mg/mL, and the ratio of the total number of molybdenum atoms in the molybdenum source to the total number of moles of sulfur atoms in the sulfur source is 1:2-1 : 6.
  • the absorbed dose rate when the mixed solution is irradiated is 30 to 30 000 Gy/min, preferably 50 to 30 000 Gy/min, and the absorbed dose may be 20,000 to 400,000 Gy, preferably 50,000 to 400,000 Gy.
  • the ⁇ -ray may specifically be 60 Co ⁇ -ray; the electron beam is generated by an electron accelerator whose energy may be 0.5-5 MeV.
  • an inert gas may be introduced into the mixed solution for removing dissolved oxygen in the mixed solution.
  • the inert gas may be selected from nitrogen, argon, or a mixed gas thereof; preferably selected from high purity nitrogen or high purity argon.
  • the high purity nitrogen or high purity argon gas refers to nitrogen or argon having a purity of 99.999% or more.
  • the separation operation may be carried out by a conventional filtration operation or by a separation method such as centrifugation; the drying temperature may be 30-60 ° C, and the time may be 12-24 hours.
  • the separated solid product is sequentially ultrasonically washed with a water-miscible alcohol and water, and then subjected to separation treatment.
  • the water-miscible alcohol is preferably ethanol.
  • the separated solid product is sequentially subjected to ultrasonic washing with a water-miscible alcohol and water, preferably deionized water, and then subjected to a separation treatment, which can be repeated 1-3 times.
  • the present application also provides the aforementioned application of the MoS x O y /carbon nanocomposite in the electrochemical hydrogen evolution reaction.
  • the MoS x O y /carbon nanocomposite can be used as a catalyst for the electrochemical hydrogen evolution reaction.
  • the present application also provides a cathode electrode for electrolyzing water to produce hydrogen (electrolyzed water to produce hydrogen is an electrochemical hydrogen evolution reaction), wherein the cathode electrode comprises a base electrode and MoS x coated on the surface of the base electrode O y / carbon nanocomposite, the base electrode is an inert electrode.
  • the base electrode may be selected from an inert electrode such as a gold electrode, a platinum electrode, a glassy carbon electrode, a graphite electrode, an ITO electrode or an FTO electrode.
  • the cathode electrode can be obtained by first dissolving a MoS x O y /carbon nanocomposite and a film forming agent (for example, a Nafion membrane solution) in a solvent, uniformly dispersing to obtain a catalyst solution; and then coating the surface of the inert electrode.
  • a film forming agent for example, a Nafion membrane solution
  • the present application also provides an electrolyzed water hydrogen production apparatus, wherein the apparatus includes the cathode electrode provided by the present application.
  • the cathode electrode provided by the present application is used in addition to the cathode electrode, and other components required for the electrolysis water hydrogen production device, such as an anode electrode and an electrolytic cell,
  • the electrolyte solution and the like can be realized by the related technical solutions in the prior art, and the present application is not limited herein.
  • the present application also provides a hydrogen fuel cell device, wherein the hydrogen fuel cell device includes a hydrogen fuel cell body and the electrolyzed water hydrogen production device provided by the present application; It is used to supply hydrogen to the hydrogen fuel cell body.
  • the structure and preparation process of the hydrogen fuel cell body are prior art. In the specific implementation process, any hydrogen fuel cell in the prior art can be used as the hydrogen fuel cell body in the present application, and the electrolyzed water provided by the present application is provided.
  • a hydrogen production unit is connected thereto for supplying hydrogen gas thereto.
  • the connection between the electrolysis water hydrogen production device and the hydrogen fuel cell body can be implemented by using the related technical solutions in the prior art, which is not limited herein.
  • the present application also provides an electric device including the hydrogen fuel cell device provided herein.
  • Other parts of the electric device other than the hydrogen fuel cell device can be implemented by the related technical solutions in the prior art, which is not limited herein.
  • the electric device includes, but is not limited to, an electric car, an electric tricycle or an electric bicycle.
  • Example 1 Preparation and application of MoS x O y /carbon nanocomposites
  • the sample was filtered through a polypropylene (PP) membrane having a pore size of 0.45 ⁇ m.
  • PP polypropylene
  • the filtered filter cake is rinsed with ethanol, filtered and then washed with deionized water, ultrasonically treated for 5 minutes each time, and then the ultrasonicated solution is filtered again, thus repeated 3 times to remove residual ethylene glycol;
  • the washed product was dried in a vacuum oven at 40 ° C for 12 hours to obtain a powdery MoS x O y /carbon nanocomposite.
  • the TEM was characterized by the prepared MoS x O y /carbon nanocomposite. The results are shown in Fig. 1. It can be seen from Fig. 1 that after radiation reduction, the particle size of the acetylene black material is about 20 nm, and MoS x In addition to the local ordered structure of the acetylene black material, the O y /carbon nanocomposite does not form an ordered oxygen-doped molybdenum sulfide structure because the radiation reduction reaction is carried out at room temperature. The mild conditions are not conducive to the arrangement of atoms in an ordered crystal structure, while the amorphous structure is more likely to expose more reactive catalytic sites than the ordered crystal structure.
  • XRD characterization of the prepared MoS x O y /carbon nanocomposites further verified that the resulting nanocomposites did not have an ordered oxygen-doped molybdenum sulfide structure, ie, the oxygen-doped molybdenum sulfide was amorphous. structure.
  • the results are shown in Fig. 2; in Fig. 2, the broadening peak of 2 ⁇ of about 22 degrees is the (002) diffraction peak of the carbon material, and the small peak of 43 degrees is the (100) diffraction peak of the carbon material, in the XRD spectrum. There are no characteristic diffraction peaks of any oxygen-doped molybdenum sulfide material.
  • the electrocatalytic hydrogen evolution reaction performance of the prepared MoS x O y /carbon nanocomposites was tested by a three-electrode system.
  • a saturated calomel electrode (SCE) was used as a reference electrode, and a 1 cm 2 Pt plate electrode was used as a counter electrode.
  • a glassy carbon electrode coated with MoS x O y /carbon nanocomposite was used as a working electrode, with a 0.5 M H. 2 SO 4 is the electrolyte, which is tested by Shanghai Chenhua's CHI 760e electrochemical workstation.
  • Test parameters linear volt-ampere test (LSV) sweep speed of 5mV / s, scan range of 0.2 ⁇ -0.4V (relative to the reversible hydrogen electrode (referred to as RHE). Cyclic voltammetry test sweep speed of 50mV / s, The scan range is 0 to -0.3 V (relative to RHE).
  • LSV linear volt-ampere test
  • RHE reversible hydrogen electrode
  • Figure 5 is a linear sweep voltammetry (LSV) diagram of the MoS x O y /carbon nanocomposite after catalytic cycling.
  • LSV linear sweep voltammetry
  • Example 1 The acetylene black in Example 1 was changed to carbon nanotubes, and other preparation conditions of the composite material were the same as in Example 1, under which the MoS x O y /carbon nanocomposite was prepared, and the mass of MoS x O y in the composite material was obtained.
  • the percentage is 17%, x is 2.91, and y is 0.58.
  • Example 1 The acetylene black in Example 1 was changed to graphite oxide, and other preparation conditions of the composite material were the same as in Example 1. Under this condition, the mass percentage of the MoS x O y /carbon nanocomposite MoS x O y in the composite material was 21%, x is 2.81, and y is 0.69.
  • Example 1 The acetylene black in Example 1 was changed to carbon nanohorn.
  • the other preparation conditions of the composite were the same as in Example 1. Under this condition, the mass of MoS x O y /carbon nanocomposite and MoS x O y in the composite were prepared. The percentage is 19%, x is 2.85, and y is 0.51.
  • Example 1 The acetylene black in Example 1 was changed to sulfonated graphite oxide, and other preparation conditions of the composite material were the same as in Example 1, under which MoS x O y /carbon nanocomposites were prepared, and MoS x O y was in the composite material.
  • the mass percentage is 24%, x is 2.83, and y is 0.56.
  • Example 1 The absorbed dose rate in Example 1 was changed to 150 Gy/min, and other preparation conditions of the composite material were the same as in Example 1, under which MoS x O y /carbon nanocomposites were prepared, and MoS x O y was in the composite material.
  • the mass percentage is 20%, x is 2.94, and y is 0.63.
  • Example 1 The absorbed dose rate in Example 1 was changed to 300 Gy/min, and other preparation conditions of the composite material were the same as in Example 1, under which MoS x O y /carbon nanocomposites were prepared, and MoS x O y was in the composite material.
  • the mass percentage is 25%, x is 3.07, and y is 0.69.
  • Example 1 The absorbed dose in Example 1 was changed to 150 kGy, and other preparation conditions of the composite material were the same as in Example 1. Under this condition, a MoS x O y /carbon nanocomposite was prepared, and the mass percentage of MoS x O y in the composite material was 24%, x is 2.81, and y is 0.45.
  • Example 1 The absorbed dose in Example 1 was changed to 300 kGy, and other preparation conditions of the composite material were the same as in Example 1, under which the MoS x O y /carbon nanocomposite was prepared, and the mass percentage of MoS x O y in the composite material was 26%, x is 2.69, and y is 0.35.
  • Example 1 The solvent in Example 1 was changed to glycerol, and other preparation conditions of the composite material were the same as in Example 1, under which the MoS x O y /carbon nanocomposite was prepared, and the mass percentage of MoS x O y in the composite material was It is 22%, x is 2.85, and y is 0.33.
  • Example 1 The solvent in Example 1 was changed to deionized water, and other preparation conditions of the composite material were the same as in Example 1, under which the MoS x O y /carbon nanocomposite was prepared, and the mass percentage of MoS x O y in the composite material was It is 24%, x is 2.81, and y is 0.45.
  • Example 1 The 20 mg of ammonium tetrathiomolybdate in Example 1 was changed to 20 mg of ammonium molybdate and 30 mg of thiourea, and the absorbed dose was changed to 200 kGy.
  • the other preparation conditions of the composite were the same as in Example 1, under which MoS x O was prepared.
  • the mass percentage of MoS x O y in the composite is 35%, x is 2.75, and y is 0.33.
  • Example 1 The 20 mg of ammonium tetrathiomolybdate in Example 1 was changed to 20 mg of ammonium molybdate and 40 mg of sodium thiosulfate, and the absorbed dose rate was changed to 1000 Gy/min, and the absorbed dose was changed to 200 kGy.
  • Example 1 a MoS x O y /carbon nanocomposite was prepared under the conditions. The mass percentage of MoS x O y in the composite was 35%, x was 2.72, and y was 0.41.
  • Example 1 The 20 mg of ammonium tetrathiomolybdate in Example 1 was changed to 20 mg of sodium molybdate and 40 mg of thiourea, and the 60 Co ⁇ -ray in Example 1 was changed to an electron beam generated by an electron accelerator.
  • the energy of the electron accelerator was 0.6 MeV.
  • the absorbed dose rate is 1000 Gy/min, the absorbed dose is changed to 200 kGy, and other preparation conditions of the composite material are the same as in Example 1, under which MoS x O y / carbon nanocomposites are prepared, and MoS x O y is in the composite material.
  • the mass percentage was 37%, x was 2.75, and y was 0.27.
  • Example 1 The 20 mg of ammonium tetrathiomolybdate in Example 1 was changed to 20 mg of sodium molybdate and 60 mg of sodium thiosulfate, and the 60 Co ⁇ -ray in Example 1 was changed to an electron beam generated by an electron accelerator.
  • the energy of the electron accelerator was 3MeV
  • the absorbed dose rate is 15kGy/min
  • the absorbed dose is changed to 400kGy
  • other preparation conditions of the composite material are the same as those in the first embodiment.
  • MoS x O y / carbon nanocomposites are prepared, and MoS x O y is in the composite material.
  • the mass percentage in the range was 35%
  • x was 2.81
  • y was 0.28.
  • Example 1 The 60 Co ⁇ -ray in Example 1 was changed to an electron beam generated by an electron accelerator.
  • the energy of the electron accelerator was 5 MeV
  • the absorbed dose rate was 30 kGy/min
  • the absorbed dose was changed to 200 kGy.
  • Other preparation conditions of the composite material were the same as in the examples. 1.
  • MoS x O y /carbon nanocomposites were prepared under these conditions.
  • the mass percentage of MoS x O y in the composite was 35%, x was 3.10, and y was 0.60.
  • Example 2-16 The catalytic performance test of the electrocatalytic hydrogen evolution reaction of the MoS x O y /carbon nanocomposite prepared in Example 2-16 was carried out according to the method and test conditions described in Example 1, and the results were recorded together with the test results of Example 1. In Table 1.
  • the corresponding overpotential refers to the overpotential at the front current density of 10 mA/cm 2 ;
  • mV/dec represents the value of the change in potential when the current density changes by an order of magnitude, and dec is the abbreviation of decade.
  • Comparative Example 1-11 According to the description in Table 2, 11 kinds of catalysts for electrocatalytic hydrogen evolution reaction were prepared, and 11 catalysts prepared in Comparative Examples 1-11 were prepared according to the method and test conditions described in Example 1. The performance of the electrocatalytic hydrogen evolution reaction was tested, and the test results are shown in Table 2. Each of the references in Table 2 is hereby incorporated by reference in its entirety herein in its entirety herein in its entirety herein in its entirety herein herein herein
  • the corresponding overpotential is the overpotential when the front current density is substantially 10 mA/cm 2
  • the MoS x O y /carbon nanocomposite prepared in the examples of the present application has a lower Tafi slope and an initial overpotential as a catalyst for the electrocatalytic hydrogen evolution reaction, and is lower.
  • the overpotential can have a large current density.
  • the current density at an overpotential of 300 mV is 150 mA/cm 2 or more, and many can reach 200 mA/cm. 2 or more, more preferably 300 mA/cm 2 or more. This performance is small or even comparable to the commercial 20% Pt/C catalyst performance (current density of 370 mA/cm 2 at an overpotential of 300 mV).
  • the current density at an overpotential of 300 mV was significantly lower than that of the present application, and the maximum current density was also less than 150 mA/cm 2 .
  • their preparation methods are relatively complicated, the material cost is relatively high, and their catalytic performance is limited, which is far from meeting the performance required for practical industrial applications.
  • the overpotential at 10 mA/cm 2 is below 200 mV
  • the material prepared in Comparative Examples 1-11 is used as a catalyst, it is over 10 mA/cm 2 .
  • the potential is mostly higher than 200mV.
  • the MoS x O y /carbon nanocomposite provided by the present application has a simple preparation method, a low cost, and an excellent catalytic performance, and can meet industrial production requirements, compared with the catalyst prepared in Comparative Examples 1-11.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Catalysts (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Fuel Cell (AREA)

Abstract

提供一种MoS xO y/碳纳米复合材料、其制备方法及其应用。在MoS xO y/碳纳米复合材料中，2.5≤x≤3.1，0.2≤y≤0.7，且基于该纳米复合材料的总质量， MoS xO y的质量百分数为5-50％。该MoS xO y/碳纳米复合材料用作电催化析氢反应催化剂时，过电势300mV时的电流密度在150mA/cm 2以上；该性能与商用的20％Pt/C催化剂性能差距较小，甚至相当，远好于现有的MoS 2复合材料的催化性能。该MoS xO y/碳纳米复合材料还具有良好的催化稳定性，在进行8000次催化循环之后，其电流密度只下降了3％，表现出了非常优良的催化性能和循环稳定性。

Description

一种MoSxOy/碳纳米复合材料、其制备方法及其应用
本申请要求于2016年07月27日提交中国专利局、申请号为201610600352.X发明名称为“一种MoSxOy/碳纳米复合材料、其制备方法及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及复合材料领域，特别涉及一种MoSxOy/碳纳米复合材料、其制备方法及其应用。
背景技术
氢气作为清洁新能源对于环境保护、能源安全都有重大的意义。如何大规模制备氢气是商业规模利用氢能源的基本问题。电化学析氢反应(Hydrogen Evolution Reaction，HER)被视为规模化制备氢气的可行方案，但是该反应在阴极上有较高的阴极过电势，从而导致制备氢气的能耗成本大幅提升。铂系贵金属作为该反应的催化剂，能够很好地降低阴极过电势，但是由于铂系贵金属在地球上的储量有限，无法满足大规模应用的需求。因此，寻找替代的催化材料，降低阴极过电势从而降低生产成本，成为研究者关注的重点内容。
二硫化钼(MoS2)是一种具有类似石墨结构的层状结构化合物。块材的二硫化钼用作HER的催化剂时具有较高的过电势，而当其层数减少到寡层乃至单层之后，其物理化学性质会发生明显的变化，研究者通过理论计算说明寡层的二硫化钼材料具有较好的HER催化活性(Berit H.，Poul G.M.，Bonde，K.P.
Figure PCTCN2017094333-appb-000001
J.Nielsen，S.Chorkendorff，J.K 
Figure PCTCN2017094333-appb-000002
Journal of the American Chemistry Society2005，127，5308-5309)。目前已有很多关于二硫化钼复合材料的文献(a，Li Y.，Wang H.，Xie L，Liang Y.，Hong G.，Dai H.，Journal of the American Chemistry Society2011，133，7296-7299；b，Bindumadhavan K.，Srivasata S.K.，Mahanty S.Chemical Communications 2013，49，(18)，1823-1825)和专利(中国发明专利ZL 201210326035.5)报道。但是目前这些研究中，二硫化钼复合材料的催化性能和铂系贵金属催化剂相比仍有较大差距。
发明内容
本申请目的在于提供一种对电化学析氢反应的催化性能优于现有的MoS2复合材料的MoSxOy/碳纳米复合材料(Mo代表钼元素，S代表硫元素，O代表氧元素)、其制备方法及其应用(在本申请中，MoSxOy也被称为氧掺杂的钼硫化物)。技术方案如下：
本申请首先提供了一种MoSxOy/碳纳米复合材料，其中，2.5≤x≤3.1，0.2≤y≤0.7。
在本申请的一种优选实施方式中，基于所述纳米复合材料的总质量，所述MoSxOy的质量百分数为5-50％。
在本申请的一种优选实施方式中，所述MoSxOy为无定型结构。
本申请还提供了前述的纳米复合材料制备方法，其中，该方法包括以下步骤：
(1)将碳源分散于溶剂中，优选地超声分散30-100分钟，得到碳源分散液；所述碳源优选选自于碳黑、碳纳米管、碳纳米角、氧化石墨、磺化氧化石墨中的至少一种；所述溶剂优选选自于乙二醇、丙三醇、水中的至少一种；
(2)将硫源和钼源加入到碳源分散液中，得到混合溶液；
(3)采用γ-射线或电子束对所述混合溶液进行辐照；辐照结束后，经分离、干燥即可得到所述纳米复合材料。
在本申请的一种优选实施方式中，所述硫源和钼源为同一化合物，且该化合物在混合溶液中的浓度为1-10mg/mL，优选1-5mg/mL，该化合物优选选自四硫代钼酸铵、四硫代钼酸钠中的至少一种。
在本申请的一种优选实施方式中，所述硫源和钼源为不同的化合物，钼源及硫源在混合溶液中的浓度为2-10mg/mL，且钼源中钼原子的总摩尔数与硫源中硫原子总摩尔数的比为1∶2-1∶6。
在本申请的一种优选实施方式中，所述硫源选自硫脲、硫代硫酸钠中的至少一种；所述钼源选自钼酸铵、五氯化钼、钼酸钠中的至少一种。
在本申请的一种优选实施方式中，碳源与溶剂的配比为1-10mg∶1mL。
在本申请的一种优选实施方式中，步骤3)中，混合溶液被辐照时的吸收剂量率为30-30000Gy/min(分钟)，吸收剂量可为20000-400000Gy。
在本申请的一种优选实施方式中，所述γ-射线为60Coγ-射线；所述电子束由能量为0.5-5MeV的电子加速器产生。在本申请的一种优选实施方式中，在步骤3)中对所述混合溶液进行辐照前，还包括向混合溶液中通入惰性气体的步骤，所述惰性气体优选为氮气、氩气或它们的混合气体。
在本申请的一种优选实施方式中，在步骤3)分离后，将分离得到的固体产物依次用与水互溶的醇和水进行超声洗涤。
本申请还提供了前述的MoSxOy/碳纳米复合材料在电化学析氢反应中的应用。
本申请提供了一种阴极电极，其中，所述阴极电极包括基底电极和涂覆在所述基底电极表面的、前述的MoSxOy/碳纳米复合材料，所述基底电极为惰性电极，优选选自金电极、铂电极、玻碳电极、石墨电极、ITO电极或FTO电极。
本申请提供了一种电解水制氢装置，其中，所述装置包括前述的阴极电极。
本申请提供了一种氢燃料电池装置，其中，所述氢燃料电池装置包括氢燃料电池本体和前述的电解水制氢装置。
本申请提供了一种电动设备，其中，所述电动设备包括前述的氢燃料电池装置，所述电动设备优选为电动汽车、电动三轮车或电动自行车。
本申请的有益效果在于：
(1)本申请选用高导电性的碳材料作为复合材料中的碳源，用辐射法制备出MoSxOy/碳纳米复合材料，其中，碳材料一方面可以增强MoSxOy/碳纳米复合材料的导电性能；另一方面碳材料形成三维网络结构有利于电解液和纳米复合材料的充分接触；另外，所生成的MoSxOy为无定型结构，增加了纳米复合材料中起催化作用的活性位点数目。而通过辐射法引入的O元素，可以提高纳米复合材料的导电性能，进一步地增强纳米复合材料的催化能力。
因此，本申请所制备的MoSxOy/碳纳米复合材料对电催化析氢反应的催化性能优于其它含有二硫化钼的催化剂的性能；且当采用本申请制备的MoSxOy/碳纳米复合材料用作电催化析氢反应催化剂时，过电势300mV时的电流密度在150mA/cm2以上，优选可以达到200mA/cm2以上，更优选可以达到300mA/cm2以上。该性能与商用的20％Pt/C催化剂性能(过电势为300mV时，电流密度370mA/cm2)差距较小，甚至相当。远好于现有的MoS2复合材料的催化性能。另外本申请制备的MoSxOy/碳纳米复合材料还具有良好的催化稳定性，在进行8000次催化循环之后，在过电势为300mV时其电流密度只下降了3％，表现出了非常优良的催化性能和循环稳定性。
(2)相对于传统的气相沉积或者水热/溶剂热法，辐射法所采用的制备装置简单，反应条件温和，操作简单，重复性好，能耗低，环境污染小，适用性强，可进行宏量制备，有良好的工业应用前景。
附图说明
为了更清楚地说明本申请实施例和现有技术的技术方案，下面对实施例和现有技术中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为实施例1制备的MoSxOy/碳纳米复合材料的透射电子显微镜(TEM)图；
图2为实施例1制备的MoSxOy/碳纳米复合材料的X射线衍射(XRD)图；
图3为实施例1制备的MoSxOy/碳纳米复合材料的X射线光电子能谱(XPS)图；其中图3A为Mo的XPS高分辨图；图3B为S的XPS高分辨图；
图4为实施例1制备的MoSxOy/碳纳米复合材料在玻碳电极上不同负载量的线性扫描伏安测试(LSV)图；
图5为实施例1制备的MoSxOy/碳纳米复合材料经过催化循环之后的线性扫描伏安测试(LSV)图。
具体实施方式
本申请首先提供了一种MoSxOy/碳纳米复合材料，其中，2.5≤x≤3.1，0.2≤y≤0.7，优选地，2.6≤x≤3.1，0.25≤y≤0.7。在本申请的具体实施方式中， 基于所述纳米复合材料的总质量，MoSxOy的质量百分数为5-50％，优选为15-40％。在本申请的具体实施方式中，所述MoSxOy为无定型结构，相对于有序的晶体结构，无定型结构的MoSxOy更容易暴露出更多的反应催化活性位点。
本申请还提供了前述的纳米复合材料制备方法，其中，该方法包括以下步骤：
(1)将碳源分散于溶剂中，优选地超声分散30-100分钟，得到碳源分散液；
在步骤(1)具体实施过程中，碳源与溶剂的配比为1-10mg∶1mL；碳源优选选自于炭黑、碳纳米管、碳纳米角、氧化石墨、磺化氧化石墨中的至少一种；所述溶剂优选选自于乙二醇、丙三醇、水优选为去离子水中的至少一种；具体实施过程中，超声分散更优选为60-100分钟；超声功率可以为500-1200W。
(2)将硫源和钼源加入到碳源分散液中，得到混合溶液；
在步骤(2)具体实施过程中，硫源和钼源可以为同一化合物，也可以为不同的化合物；当硫源和钼源为同一化合物时，即该化合物既包含硫元素又包含钼元素，该化合物包括但不限于四硫代钼酸铵或四硫代钼酸钠或其组合。具体实施过程中，这种既包含硫元素又包含钼元素的化合物在混合溶液中的浓度可以为1-10mg/mL，优选1-5mg/mL。当硫源和钼源为不同的化合物时，硫源包括但不限于硫脲、硫代硫酸钠中的至少一种，钼源包括但不限于钼酸铵、五氯化钼、钼酸钠中的至少一种；钼源及硫源在混合溶液中的浓度为2-10mg/mL，且钼源中钼原子的总摩尔数与硫源中硫原子总摩尔数的比为1∶2-1∶6。
(3)采用γ-射线或电子束对所述混合溶液进行辐照；辐照结束后，经分离、干燥即可得到所述纳米复合材料。
在步骤(3)具体实施过程中，混合溶液被辐照时的吸收剂量率为30-30000Gy/min，优选为50-30000Gy/min，吸收剂量可为20000-400000Gy，优选为50000-400000Gy。其中，所述γ-射线具体可以为60Coγ-射线；所述电子束由能量可以为0.5-5MeV的电子加速器产生。优选地，对所述混合溶液进行辐照 前，还可以向混合溶液中通入惰性气体，用于除去混合溶液中的溶解氧。其中，所述惰性气体可以选自于氮气、氩气，或它们的混合气体；优选选自于高纯氮气或高纯氩气。所说的高纯氮气或高纯氩气指的是纯度为99.999％以上的氮气或氩气。分离操作可以采用常规的过滤操作，也可以采用离心等分离方式；干燥的温度可以为30-60℃，时间可以为12-24小时。
优选地，在步骤(3)分离后，将分离得到的固体产物依次用与水互溶的醇和水进行超声洗涤，再进行分离处理。所说的与水互溶的醇优选为乙醇。在实际具体实施时，可能需要多次重复上述洗涤-过滤操作，以除去步骤(1)中所引入的溶剂。一般地，将分离得到的固体产物依次用与水互溶的醇和水优选为去离子水进行超声洗涤，再进行分离处理这一步骤，可以重复进行1-3次。
本申请还提供了前述的MoSxOy/碳纳米复合材料在电化学析氢反应中的应用，具体而言，MoSxOy/碳纳米复合材料可以作为电化学析氢反应的催化剂。
本申请还提供了一种阴极电极，该阴极电极用于电解水制氢(电解水制氢是电化学析氢反应)，其中，该阴极电极包括基底电极和涂覆在该基底电极表面的MoSxOy/碳纳米复合材料，基底电极为惰性电极，具体实施过程中，基底电极可以选自金电极、铂电极、玻碳电极、石墨电极、ITO电极或FTO电极等惰性电极。
该阴极电极可以由以下方法制得：先将MoSxOy/碳纳米复合材料和成膜剂(例如Nafion膜溶液)溶解于溶剂中，分散均匀，得到催化剂溶液；然后向惰性电极表面涂覆该催化剂溶液并干燥即可。
本申请还提供了一种电解水制氢装置，其中，该装置包括本申请所提供的阴极电极。需要说明的是，对于本申请所提供的电解水制氢装置而言，除阴极电极采用本申请提供的阴极电极，其它组成电解水制氢装置所需要的各部件，例如阳极电极、电解槽及电解液等，均可以采用现有技术中的相关技术方案来实现，本申请在此不进行限定。
本申请还提供了一种氢燃料电池装置，其中，该氢燃料电池装置包括氢燃料电池本体和本申请提供的电解水制氢装置；本申请提供的电解水制氢装 置用于向氢燃料电池本体提供氢气。氢燃料电池本体的结构及制备工艺是现有技术，在具体实施过程中，可以采用现有技术中的任意的氢燃料电池作为本申请中的氢燃料电池本体，并将本申请提供的电解水制氢装置与其相连，用于向其提供氢气。将电解水制氢装置和氢燃料电池本体的连接方式可以采用现有技术中的相关技术方案实现，本申请在此不进行限定。
本申请还提供了一种电动设备，该电动设备包括本申请提供的氢燃料电池装置。电动设备除氢燃料电池装置外的其它部分可以采用现有技术中的相关技术方案实现，本申请在此不进行限定。在本申请中，所说的电动设备包括但不限于电动汽车、电动三轮车或电动自行车。
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅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作出创造性劳动前提下所获得的所有其它实施例，都属于本申请保护的范围。
下述实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1：MoSxOy/碳纳米复合材料的制备和应用
制备MoSxOy/碳纳米复合材料
将80mg乙炔黑分散到20ml乙二醇中(4mg/mL)，室温条件下用超声波处理器超声分散60分钟(超声功率650W)，得到乙炔黑分散液；随后，加入40mg四硫代钼酸铵，得到混合溶液；转移至辐射管中，通入高纯氮气30分钟，用橡胶塞密封后于60Coγ-射线辐射装置中在室温下进行辐照，剂量率为50Gy/min，吸收剂量为50kGy。辐照完毕后，将样品用孔径0.45μm的聚丙烯(PP)膜过滤。过滤后的滤饼用乙醇淋洗，过滤后再用去离子水洗涤，每次洗涤时用超声波处理5分钟然后将超声后的溶液再过滤，如此反复3次，以去除残留的乙二醇；将洗涤后的产物在真空烘箱中40℃干燥12小时得到粉末状的MoSxOy/碳纳米复合材料。
对所制备的MoSxOy/碳纳米复合材料进行TEM表征，结果如图1所示；从图1可以看出，经过辐射还原后，乙炔黑材料的粒径尺寸为20nm左右，而MoSxOy/碳纳米复合材料中除了乙炔黑材料存在局部有序结构外，并没有生成有序的氧掺杂的钼硫化物结构，这是因为辐射还原的反应是在室温下进行的，在这样的温和条件下不利于原子排布为有序的晶体结构，而相对于有序的晶体结构，无定型结构更易暴露出更多的反应催化活性位点。
对所制备的MoSxOy/碳纳米复合材料进行XRD表征，进一步验证了生成的纳米复合材料不存在有序的氧掺杂的钼硫化物结构，即氧掺杂的钼硫化物为无定型结构。结果如图2所示；在图2中，2θ为22度左右的宽化峰为碳材料的(002)衍射峰，43度的小峰为碳材料的(100)衍射峰，在XRD谱图中并没有出现任何氧掺杂的钼硫化物材料的特征衍射峰。
对所制备的MoSxOy/碳纳米复合材料进行XPS表征，结果如图3A和图3B所示；从图3A中可以看出，四硫代钼酸铵中的钼被还原生成了Mo4+，同时存在Mo-S键和Mo-O键，从图3B可以看到材料中同时存在52 2-和S2-。通过电感耦合等离子体原子发射光谱(ICP-AES)确定MoSxOy在MoSxOy/碳复合材料中的质量百分数为15％，x为2.89，结合XPS的结果，y为0.58。
MoSxOy/碳纳米复合材料催化性能测试
采用三电极体系对制备的MoSxOy/碳纳米复合材料电催化析氢反应性能进行测试。以饱和甘汞电极(SCE)为参比电极，1cm2的Pt片电极作为对电极，以表面涂覆有MoSxOy/碳纳米复合材料的玻碳电极作为工作电极，以0.5M的H2SO4为电解液，采用上海辰华的CHI 760e型电化学工作站进行测试。
采用滴涂法制备工作电极，具体方法如下：称取4mg MoSxOy/碳纳米复合材料分散于1ml超纯水/乙醇(V水∶V乙醇＝4∶1)的混合溶剂中，然后加入40μL5％的Nafion膜溶液，常温条件下用超声波处理器超声分散30分钟以上获得均一的催化剂溶液，向已经打磨光滑的直径为3mm的L型玻碳电极表面分别滴涂2、3、4、5、6、8μL上述催化剂溶液，待表面彻底干燥后形成催化剂负载量为0.110、0.165、0.220、0.275、0.330、0.440mg/cm2的工作电极，将其 用于线性扫描伏安测试(LSV)，测试结果如图4和图5所示。
测试参数：线性伏安测试(LSV)时扫速为5mV/s，扫描范围为0.2～-0.4V(相对于可逆氢电极(简称RHE)。循环伏安测试时其扫速为50mV/s，扫描范围为0～-0.3V(相对于RHE)。
从图4可以看到，催化剂在玻碳电极上的负载量从0.110mg/cm2提高到0.330mg/cm2时，电流密度也随之提高，说明在这个负载量范围内，提高催化剂的负载量能够提高催化能力，但是电流密度提高的程度并不和催化剂的含量成正比，说明催化剂的利用率下降，而随着催化剂负载量继续增加，催化剂过多，可能阻碍了析氢反应的质子与催化剂表面的传质步骤，从而导致催化剂的利用率继续下降，电流密度下降。
图5为MoSxOy/碳纳米复合材料经过催化循环之后的线性扫描伏安测试(LSV)图，从图5可以看出，MoSxOy/C复合材料具有非常好的催化稳定性。当进行8000次催化循环之后，在过电势为300mV的条件下，其电流密度只下降了3％。复合材料对HER反应的催化起始电压有稍许上升，这是由于在催化过程中有部分活性位点失活导致。
实施例2：MoSxOy/碳纳米复合材料的制备
将实施例1中的乙炔黑改为碳纳米管，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为17％，x为2.91，y为0.58。
实施例3：MoSxOy/碳纳米复合材料的制备
将实施例1中的乙炔黑改为氧化石墨，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料MoSxOy在复合材料中的质量百分数为21％，x为2.81，y为0.69。
实施例4：MoSxOy/碳纳米复合材料的制备
将实施例1中的乙炔黑改为碳纳米角，复合材料的其它制备条件同实施 例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为19％，x为2.85，y为0.51。
实施例5：MoSxOy/碳纳米复合材料的制备
将实施例1中的乙炔黑改为磺化氧化石墨，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为24％，x为2.83，y为0.56。
实施例6：MoSxOy/C纳米复合材料的制备
将实施例1中的吸收剂量率改为150Gy/min，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为20％，x为2.94，y为0.63。
实施例7：MoSxOy/C纳米复合材料的制备
将实施例1中的吸收剂量率改为300Gy/min，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为25％，x为3.07，y为0.69。
实施例8：MoSxOy/碳纳米复合材料的制备
将实施例1中的吸收剂量改为150kGy，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为24％，x为2.81，y为0.45。
实施例9：MoSxOy/碳纳米复合材料的制备
将实施例1中的吸收剂量改为300kGy，复合材料的其它制备条件同实施 例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为26％，x为2.69，y为0.35。
实施例10：MoSxOy/碳纳米复合材料的制备
将实施例1中的溶剂改为丙三醇，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为22％，x为2.85，y为0.33。
实施例11：MoSxOy/碳纳米复合材料的制备
将实施例1中的溶剂改为去离子水，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为24％，x为2.81，y为0.45。
实施例12：MoSxOy/碳纳米复合材料的制备
将实施例1中的20mg四硫代钼酸铵改为20mg钼酸铵和30mg硫脲，将吸收剂量改为200kGy，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为35％，x为2.75，y为0.33。
实施例13：MoSxOy/碳纳米复合材料的制备
将实施例1中的20mg四硫代钼酸铵改为20mg钼酸铵和40mg硫代硫酸钠，将吸收剂量率改为1000Gy/min，吸收剂量改为200kGy，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为35％，x为2.72，y为0.41。
实施例14：MoSxOy/碳纳米复合材料的制备
将实施例1中的20mg四硫代钼酸铵改为20mg钼酸钠和40mg硫脲，将实施例1中的60Coγ-射线改为电子加速器产生的电子束，电子加速器的能量为0.6MeV，其吸收剂量率为1000Gy/min，吸收剂量改为200kGy，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为37％，x为2.75，y为0.27。
实施例15：MoSxOy/碳纳米复合材料的制备
将实施例1中的20mg四硫代钼酸铵改为20mg钼酸钠和60mg硫代硫酸钠，将实施例1中的60Coγ-射线改为电子加速器产生的电子束，电子加速器的能量为3MeV，其吸收剂量率为15kGy/min，吸收剂量改为400kGy，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为35％，x为2.81，y为0.28。
实施例16：MoSxOy/碳纳米复合材料的制备
将实施例1中的60Coγ-射线改为电子加速器产生的电子束，电子加速器的能量为5MeV，其吸收剂量率为30kGy/min，吸收剂量改为200kGy，复合材料的其它制备条件同实施例1，在此条件下制备MoSxOy/碳纳米复合材料，MoSxOy在复合材料中的质量百分数为35％，x为3.10，y为0.60。
需要说明的是，在上述各实施例中，1kGy＝1000Gy。
按照实施例1中记载的方法和测试条件对实施例2-16所制备的MoSxOy/碳纳米复合材料进行电催化析氢反应的催化性能测试，将结果与实施例1的测试结果一同记载于表1中。
表1 实施例1-16制备的MoSxOy/碳纳米复合材料的催化性能比较
Figure PCTCN2017094333-appb-000003
Figure PCTCN2017094333-appb-000004
a，对应的过电势是指前列电流密度为10mA/cm2时的过电势；mV/dec表示当电流密度变化一个数量级时电势的变化的值，dec是decade的缩写。
对比例1-11：根据表2中参考文献的记载，制备出11种电催化析氢反应的催化剂，并按照实施例1中记载的方法和测试条件对对比例1-11所制备的11种催化剂进行电催化析氢反应性能进行测试，并将测试结果记载于表2中。其中，表2中各参考文献均通过引用其全文并入本申请中，本申请在此不进行赘述。
表2 对比例1-11制备的催化剂的催化性能比较
Figure PCTCN2017094333-appb-000005
Figure PCTCN2017094333-appb-000006
a，对应的过电势是指前列电流密度基本为10mA/cm2时的过电势
b，这些数据经过了iR校正
表2中各参考文献如下：
1，Xie J.，Zhang H.，Li S.，Wang R.，Sun X.，Zhou M.，Zhou J.，Lou X.，Xie Y.Advanced Materials 2013，25(40)，5807-5813。
2，Benck J.D.，Chen Z.，Kuritzky L.Y.，Forman A.J.，Jaramillo T.F.ACS Catalysis 2012，2(9)，1916-1923。
3，Lukowski M.A.，Daniel A.S.，Meng F.，Forticaux A.，Li L.，Jin S.，Journal of the American Chemical Society 2013，135(28)，10274-10277。
4，Benson J.，Li M.，Wang S.，Wang P.，Papakonstantinou P.ACS Applied Materials & Interfaces 2015，7(25)，14113-14122。
5，Guo B.，Yu K.，Li H.，Song H.，Zhang Y.，Lei X.，Fu H.，Tan Y.，Zhu Z.ACS Applied Materials & Interfaces 2016，8(8)，5517-5525。
6，Li Y.，Wang H.，Xie L.，Liang Y.，Hong G.，Dai H.Journal of the American Chemical Society 2011，133(19)，7296-7299。
7，Zhao Y.，Xie X.，Zhang J.，Liu H.，Ahn H.，Sun K.，Wang G.Chemistry-A European Journal 2015，21(45)，15908-15913。
8，Kibsgaard J.，Chen Z.，Reinecke B.N.，Jaramillo T.F.Nature Materials2012，11(11)，963-969。
9，Wang T.，Liu L.，Zhu Z.，Papakonstantinou P.，Hu J.，Liu H.，Li M.Energy & Environmental Science 2013，6(2)，625-633。
10，Shi Y.Wang J.，WangC.，Zhai T.，Bao W.，Xu J.，Xia X.，Chen H.Journal of the American Chemical Society 2015，137(23)，7365-7370。
11，Zheng X.，Xu J.，Yan K.，Wang H.，Wang Z.，Yang S.Chemistry of Materials 2014，26(7)，2344-2353。
综合分析表1和表2可知，本申请实施例制备的MoSxOy/碳纳米复合材料作为电催化析氢反应的催化剂时，具有较低的塔菲斜率和起始过电势，并在较低的过电势下就能具有很大的电流密度，例如本申请实施例1-16所制备的材料作为催化剂时，过电势300mV时的电流密度在150mA/cm2以上，很多都可以达到200mA/cm2以上，更好的可以达到300mA/cm2以上。该性能与商用的20％Pt/C催化剂性能(过电势为300mV时，电流密度370mA/cm2)差距较小，甚至相当。
而对比例1-11所制备的催化剂，过电势300mV时的电流密度显著低于本申请实施例，最大的电流密度也小于150mA/cm2。而且它们的制备方法较为复杂，材料成本较为高昂，同时其催化性能有限，远不能满足实际工业应用所需要达到的性能。
另外，本申请实施例所制备的材料作为催化剂时，其10mA/cm2时的过电势均在200mV以下，而对比例1-11所制备的材料作为催化剂时，其10mA/cm2时的过电势大多高于200mV。
可见，本申请所提供的MoSxOy/碳纳米复合材料与对比例1-11所制备的催化剂相比制备方法简单，成本低廉，同时具有优异的催化性能，可满足工业生产需求。
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。

Claims (14)

  1. 一种MoSxOy/碳纳米复合材料，其中，2.5≤x≤3.1，0.2≤y≤0.7。
  2. 如权利要求1所述的纳米复合材料，其中，基于所述纳米复合材料的总质量，所述MoSxOy的质量百分数为5-50％，优选地，所述MoSxOy为无定型结构。
  3. 如权利要求1-2中任一项所述的纳米复合材料的制备方法，其中，该方法包括以下步骤：
    (1)将碳源分散于溶剂中，优选地超声分散30-100分钟，得到碳源分散液；所述碳源优选选自于碳黑、碳纳米管、碳纳米角、氧化石墨、磺化氧化石墨中的至少一种；所述溶剂优选选自于乙二醇、丙三醇、水中的至少一种；
    (2)将硫源和钼源加入到碳源分散液中，得到混合溶液；
    (3)采用γ-射线或电子束对所述混合溶液进行辐照；辐照结束后，经分离、干燥即可得到所述纳米复合材料。
  4. 如权利要求3所述的纳米复合材料的制备方法，其中，所述硫源和钼源为同一化合物，且该化合物在混合溶液中的浓度为1-10mg/mL，优选1-5mg/mL，该化合物优选选自四硫代钼酸铵、四硫代钼酸钠中的至少一种；
    或
    所述硫源和钼源为不同的化合物，钼源及硫源在混合溶液中的浓度为2-10mg/mL，且钼源中钼原子的总摩尔数与硫源中硫原子总摩尔数的比为1∶2-1∶6，优选地，所述硫源选自硫脲、硫代硫酸钠中的至少一种；所述钼源选自钼酸铵、五氯化钼、钼酸钠中的至少一种。
  5. 如权利要求3所述的纳米复合材料的制备方法，其中，碳源与溶剂的配比为1-10mg∶1mL。
  6. 如权利要求3所述的纳米复合材料的制备方法，其中，步骤3)中，混合溶液被辐照时的吸收剂量率为30-30000Gy/min，吸收剂量为20000-400000Gy。
  7. 如权利要求3所述的纳米复合材料的制备方法，其中，所述γ-射线为 60Coγ-射线；所述电子束由能量为0.5-5MeV的电子加速器产生。
  8. 如权利要求3-7中任一项所述的方法，其中，在步骤3)中对所述混合溶液进行辐照前，还包括向混合溶液中通入惰性气体的步骤，所述惰性气体优选为氮气、氩气或它们的混合气体。
  9. 如权利要求3-7中任一项所述的方法，其中，在步骤3)分离后，将分离得到的固体产物依次用与水互溶的醇和水进行超声洗涤。
  10. 如权利要求1-2中任一项所述的MoSxOy/碳纳米复合材料在电化学析氢反应中的应用。
  11. 一种阴极电极，其中，所述阴极电极包括基底电极和涂覆在所述基底电极表面的、如权利要求1-2中任一项所述的MoSxOy/碳纳米复合材料，所述基底电极为惰性电极，优选选自金电极、铂电极、玻碳电极、石墨电极、ITO电极或FTO电极。
  12. 一种电解水制氢装置，其中，所述装置包括如权利要求11所述的阴极电极。
  13. 一种氢燃料电池装置，其中，所述氢燃料电池装置包括氢燃料电池本体和权利要求12所述的电解水制氢装置。
  14. 一种电动设备，其中，所述电动设备包括权利要求13所述的氢燃料电池装置，所述电动设备优选为电动汽车、电动三轮车或电动自行车。
PCT/CN2017/094333 2016-07-27 2017-07-25 一种MoSxOy/碳纳米复合材料、其制备方法及其应用 Ceased WO2018019234A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/320,450 US11349116B2 (en) 2016-07-27 2017-07-25 MoSxOy/carbon nanocomposite material, preparation method therefor and use thereof
JP2019503982A JP6814996B2 (ja) 2016-07-27 2017-07-25 ＭｏＳｘＯｙ／カーボンナノコンポジット材料、その調製方法およびその使用
EP17833537.8A EP3511297B1 (en) 2016-07-27 2017-07-25 Mosxoy/carbon nanocomposite material, preparation method therefor and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610600352.X 2016-07-27
CN201610600352.XA CN107010670B (zh) 2016-07-27 2016-07-27 一种MoSxOy/碳纳米复合材料、其制备方法及其应用

Publications (1)

Publication Number Publication Date
WO2018019234A1 true WO2018019234A1 (zh) 2018-02-01

Family

ID=59439390

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/094333 Ceased WO2018019234A1 (zh) 2016-07-27 2017-07-25 一种MoSxOy/碳纳米复合材料、其制备方法及其应用

Country Status (5)

Country Link
US (1) US11349116B2 (zh)
EP (1) EP3511297B1 (zh)
JP (1) JP6814996B2 (zh)
CN (1) CN107010670B (zh)
WO (1) WO2018019234A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113603161A (zh) * 2021-09-08 2021-11-05 安阳师范学院 一种高性能镍铝层状双硫化物／氧化物复合电极材料的制备方法
CN116002755A (zh) * 2022-12-26 2023-04-25 中国科学院山西煤炭化学研究所 一种制备金属元素改性钼基氧硫复合物的方法

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107474400B (zh) * 2017-07-31 2020-09-04 威固技术（安徽）有限公司 一种改善汽车nvh性能自润滑橡胶吊耳及其制备方法
CN107934939A (zh) * 2017-11-14 2018-04-20 中山大学 一种层数可控MoS2/碳纳米管复合材料的制备方法
CN108273524B (zh) * 2017-12-27 2021-04-23 温州大学 一种硫属化合物与过渡金属修饰的碳复合材料及其制备方法与应用
CN108517534B (zh) * 2018-03-09 2020-06-23 三峡大学 一种cvd方法制备多功能的镍掺杂二硫化钼原位电极
CN108411322B (zh) * 2018-03-09 2020-06-23 三峡大学 一种硫化钴与二硫化钼原位复合电极的制备方法及其在水电解制氢上的应用
CN108396330B (zh) * 2018-03-09 2020-06-23 三峡大学 一种二硫化钼纳米片@硫化钴纳米针原位阵列电极的制备方法
CN108385132B (zh) * 2018-03-09 2020-06-23 三峡大学 一种Co掺杂MoS2阵列原位电极的CVD制备方法
CN108816250B (zh) * 2018-06-06 2020-02-18 北京师范大学 一种纳米棒阵列复合材料及其制备方法和应用
CN111250119B (zh) * 2020-01-22 2021-04-30 北京大学 一种导电基材表面生长CoPxOy纳米阵列复合材料及其制备和应用
CN111447821B (zh) * 2020-05-18 2022-06-21 哈尔滨工业大学 一种碳化物/碳纳米复合材料的制备方法
CN114345374B (zh) * 2020-09-27 2024-03-08 武汉理工大学 一种碳布上构筑的非晶态多硫化钼析氢电催化剂的制备方法
CN112331834B (zh) * 2020-11-12 2021-07-16 郑州轻工业大学 一种灯泡状O-MXn/C纳米反应器及其制备方法和应用
CN113529126B (zh) * 2021-06-18 2022-08-23 复旦大学 一种催化活性物种含量可控的非晶硫化钼/石墨烯催化剂及其制备和应用
CN113713833B (zh) * 2021-09-15 2022-10-28 北京师范大学 钼氧硫化物/硫化镍/泡沫镍复合体及其制备方法和应用
CN114149028B (zh) * 2021-11-15 2022-09-06 大连理工大学 一种乙二醇诱导氧掺杂二硫化钼方法及其在锂硫电池中的应用
CN117049521B (zh) * 2023-07-21 2025-07-01 华中科技大学 一种MoS2修饰氮掺杂碳纳米片复合材料及其制备与应用
CN118022811B (zh) * 2024-04-02 2025-10-31 重庆工商大学 一种10% Co@MoS2/MoO3-x/C3N4光催化剂在光催化氨硼烷水解产氢上的应用
FR3162053A1 (fr) * 2024-05-13 2025-11-14 IFP Energies Nouvelles Procédé de préparation d’une électrode activée électrochimiquement à base de MoS2 supporté pour des réactions de réduction électrochimique

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105200450A (zh) * 2015-09-10 2015-12-30 北京航空航天大学 一种二硫化钼/炭黑复合析氢电催化材料及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2377971A1 (en) * 2010-04-16 2011-10-19 EPFL Ecole Polytechnique Fédérale de Lausanne Amorphous transition metal sulphide films or solids as efficient electrocatalysts for hydrogen production from water or aqueous solutions
JP2012119078A (ja) 2010-11-29 2012-06-21 Asahi Glass Co Ltd 蓄電デバイス用電極合剤の製造方法
CN102142537B (zh) 2011-02-25 2015-03-25 浙江大学 一种石墨烯/MoS2复合纳米材料锂离子电池电极及制备方法
KR20140008205A (ko) 2012-07-11 2014-01-21 김동훈 미끄럼 베어링 소재 제조 방법
CN103000887A (zh) 2012-11-06 2013-03-27 苏州懿源宏达知识产权代理有限公司 一种离子电池石墨硫化钼纳米复合负极材料的制备方法
CN104525185B (zh) * 2014-12-26 2016-07-13 清华大学 一种碳基复合物燃料电池阴极氧还原催化剂及其制备方法
CN105098151B (zh) 2015-06-19 2017-05-24 上海交通大学 一种二硫化钼‑碳空心球杂化材料及其制备方法
CN105680060B (zh) * 2016-02-23 2018-05-15 东华大学 一种氮、硫或氯掺杂三维多孔石墨烯催化剂的制备及应用
CN106960948B (zh) 2016-07-27 2020-07-10 北京大学 一种MoSx/碳黑纳米复合材料、其制备方法及其应用

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105200450A (zh) * 2015-09-10 2015-12-30 北京航空航天大学 一种二硫化钼/炭黑复合析氢电催化材料及其制备方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
LAI, GUOHONG ET AL.: "Electronic Structure and Photoelectric Properties of O-and Se-doped Single-layer MoS2", MATERIALS REVIEW, vol. 29, no. 9, 30 September 2015 (2015-09-30), pages 152 - 155, XP009511769 *
LI, DONGJUN ET AL.: "Molybdenum Sulfide/N-Doped CNT Forest Hybrid Catalysts for High-Performance Hydrogen Evolution Reaction", NANO LETTERS, 16 February 2014 (2014-02-16), pages 1228 - 1233, XP055461542 *
XIE, JUNFENG ET AL.: "Function-oriented design and electrochemical properties of two-dimensional crystals", CHINA DOCTORAL DISSERTATION, 15 October 2014 (2014-10-15), pages 1 - 128, XP009512609 *
XIE, JUNFENG ET AL.: "Vertically aligned oxygen-doped molybdenum disulfide nanosheets grown on carbon cloth realizing robust hydrogen evolution reaction", INORGANIC CHEMISTRY FRONTIERS, 19 July 2016 (2016-07-19), pages 1160 - 1166, XP055461539, DOI: 10.1039/C6QI00198J *
ZHAO, XIAOXUAN: "Controlled synthesis and hydrogen evolution catalysis research of MoS2 composites", SCIENCE -ENGINEERING (A) , CHINA MASTER'S THESES DATABASE, 15 July 2016 (2016-07-15), pages 1 - 78, XP009515780 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113603161A (zh) * 2021-09-08 2021-11-05 安阳师范学院 一种高性能镍铝层状双硫化物／氧化物复合电极材料的制备方法
CN116002755A (zh) * 2022-12-26 2023-04-25 中国科学院山西煤炭化学研究所 一种制备金属元素改性钼基氧硫复合物的方法
CN116002755B (zh) * 2022-12-26 2023-10-24 中国科学院山西煤炭化学研究所 一种制备金属元素改性钼基氧硫复合物的方法

Also Published As

Publication number Publication date
EP3511297A1 (en) 2019-07-17
EP3511297B1 (en) 2020-08-26
US11349116B2 (en) 2022-05-31
US20190237751A1 (en) 2019-08-01
CN107010670A (zh) 2017-08-04
EP3511297A4 (en) 2019-07-17
CN107010670B (zh) 2018-10-16
JP2019531402A (ja) 2019-10-31
JP6814996B2 (ja) 2021-01-20

Similar Documents

Publication Publication Date Title
CN107010670B (zh) 一种MoSxOy/碳纳米复合材料、其制备方法及其应用
CN106960948B (zh) 一种MoSx/碳黑纳米复合材料、其制备方法及其应用
Modak et al. Metal–organic polymer-derived interconnected Fe–Ni alloy by carbon nanotubes as an advanced design of urea oxidation catalysts
Li et al. Template-directed bifunctional dodecahedral CoP/CN@ MoS2 electrocatalyst for high efficient water splitting
Xiao et al. Engineering NiS/Ni2P heterostructures for efficient electrocatalytic water splitting
Shi et al. Ni2P nanosheets/Ni foam composite electrode for long-lived and pH-tolerable electrochemical hydrogen generation
Chang et al. Enhanced electrocatalytic activity of MoS x on TCNQ-treated electrode for hydrogen evolution reaction
Guo et al. Few-layered trigonal WS2 nanosheet-coated graphite foam as an efficient free-standing electrode for a hydrogen evolution reaction
CN110252335B (zh) 一种碳包覆镍钌纳米材料及其制备方法和应用
Berglund et al. p-Si/W2C and p-Si/W2C/Pt photocathodes for the hydrogen evolution reaction
Zhu et al. Ultrafine metal phosphide nanocrystals in situ decorated on highly porous heteroatom-doped carbons for active electrocatalytic hydrogen evolution
Cheng et al. Strongly coupling of amorphous/crystalline reduced FeOOH/α-Ni (OH) 2 heterostructure for extremely efficient water oxidation at ultra-high current density
Hou et al. Graphene dots embedded phosphide nanosheet-assembled tubular arrays for efficient and stable overall water splitting
CN111346642B (zh) 高分散金属纳米颗粒/生物质碳复合电极材料及其制备方法与应用
Guan et al. Understanding the enhanced electrocatalytic hydrogen evolution via integrating electrochemically inactive g-C3N4: the effect of interfacial engineering
Xu et al. Heterogeneous synergetic effect of metal–oxide interfaces for efficient hydrogen evolution in alkaline solutions
Maity et al. MoSe2-amorphous CNT hierarchical hybrid core–shell structure for efficient hydrogen evolution reaction
Jiang et al. Selective growth of vertically aligned two-dimensional MoS2/WS2 nanosheets with decoration of Bi2S3 nanorods by microwave-assisted hydrothermal synthesis: enhanced photo-and electrochemical performance for hydrogen evolution reaction
Yuan et al. Ultrathin MoSe2 nanosheets coated on hollow carbon spheres as efficient hybrid catalyst for hydrogen evolution reaction
Guo et al. Walnut-like transition metal carbides with three-dimensional networks by a versatile electropolymerization-assisted method for efficient hydrogen evolution
Li et al. Hollow bimetallic cobalt-based selenide polyhedrons for efficient hydrogen production in practical PEM electrolysis
Ning et al. Modified Si nanowire/graphite-like carbon nitride core-shell photoanodes for solar water splitting
Fan et al. Photoassisted Electrochemical Hydrogen Evolution Reaction of MFe2O4@ Ultrathin Black Phosphorus Amorphous–Crystalline Interface
Cheng et al. Engineering Amorphous/Crystalline Ru (OH) 3/CoFe-Layered Double Hydroxide for Hydrogen Evolution at 1000 mA cm–2
Liao et al. Microwave-polyol synthesis and electrocatalytic performance of Pt/graphene nanocomposites

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17833537

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019503982

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017833537

Country of ref document: EP

Effective date: 20190212