WO2024234792A1 - 一种MoS2-Pd氢敏材料及其制备方法 - Google Patents

一种MoS2-Pd氢敏材料及其制备方法 Download PDF

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WO2024234792A1
WO2024234792A1 PCT/CN2024/080705 CN2024080705W WO2024234792A1 WO 2024234792 A1 WO2024234792 A1 WO 2024234792A1 CN 2024080705 W CN2024080705 W CN 2024080705W WO 2024234792 A1 WO2024234792 A1 WO 2024234792A1
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hydrogen
sensitive material
mos
film
mos2
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French (fr)
Inventor
平小凡
刘明义
曹曦
曹传钊
林伟杰
宋太纪
雷浩东
孙周婷
杨超然
成前
赵珈卉
白盼星
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China Hua Neng Group Hong Kong Ltd
Huaneng Clean Energy Research Institute
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China Hua Neng Group Hong Kong Ltd
Huaneng Clean Energy Research Institute
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • 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

Definitions

  • the present disclosure belongs to the technical field of hydrogen sensors, and in particular relates to a MoS 2 -Pd hydrogen-sensitive material and a preparation method thereof.
  • Hydrogen energy has the advantages of wide distribution, clean and renewable, high energy density and wide application, and is considered to be an ideal energy source to replace fossil fuels.
  • hydrogen is a colorless and odorless flammable gas with low ignition energy. It is very easy to explode when encountering open flames or electric currents. At the same time, it is easy to leak during production, storage and transportation, posing serious safety hazards. Therefore, it is of great significance to detect hydrogen in a timely, accurate and sensitive manner.
  • Fiber Bragg grating hydrogen sensors have the advantages of small size, long life, intrinsic safety, anti-electromagnetic interference, high sensitivity, etc. They are suitable for working in flammable and explosive environments, and have become a research hotspot in hydrogen detection technology.
  • the precious metal palladium (Pd) has specific selectivity and reversible adsorption for hydrogen, so it is widely used as a hydrogen-sensitive material in fiber Bragg grating hydrogen sensors.
  • Pd absorbs hydrogen
  • the hydride formed by Pd has ⁇ phase and ⁇ phase.
  • the embodiments of the present disclosure are intended to solve one of the technical problems in the related art at least to a certain extent.
  • the embodiments of the present disclosure provide a MoS 2 -Pd hydrogen-sensitive material and a preparation method thereof.
  • the present disclosure provides a method for preparing a MoS 2 -Pd hydrogen-sensitive material, comprising the following steps:
  • the method for preparing the conductive substrate is: evaporating a metal film on the surface of a SiO 2 /Si substrate to obtain the conductive substrate; the evaporation area of the metal film accounts for 30% to 50% of the surface area of the SiO 2 /Si substrate; the metal film is a Cr/Au metal film or a Ti/Au metal film; in the Cr/Au metal film, the thickness ratio of the Cr metal film to the Au metal film is 1:10; and the thickness of the Cr metal film is 6 to 10 nm; the thickness of the Au metal film is 60 to 100 nm; in the Ti/Au metal film, the thickness ratio of the Ti metal film to the Au metal film is 1:10; and the thickness of the Ti metal film is 6 to 10 nm; the thickness of the Au metal film is 60 to 100 nm;
  • step S5 the constant potential is -0.20 V vs SCE, and the electrochemical deposition time is 5 to 30 s.
  • Pd nanoparticles are deposited on the MoS2 film by electrochemical deposition. Since the MoS2 film has a large specific surface area and various types of defects exist on the surface, including point defects (vacancies and substitutions), dislocations and grain boundaries, etc., which can be used as active sites for the deposition of Pd2 + , the Pd2 + in the electroplating solution can be firmly deposited at the active sites on the MoS2 surface and reduced to Pd nanoparticles under constant potential.
  • the interaction between the Pd nanoparticles and the MoS2 film is strong, the problem of easy detachment of the Pd nanoparticles during the process of hydrogen absorption and release can be overcome; and the electrochemical deposition method is used to deposit Pd nanoparticles, which is more convenient to operate, and the entire preparation process is green, pollution-free, lossless and low-cost.
  • the method for growing a MoS2 thin film on a substrate is: using MoO3 and sulfur powder as reaction raw materials, growing the MoS2 thin film on the substrate by chemical vapor deposition to obtain the substrate loaded with the MoS2 thin film; the molar ratio of the MoO3 to the sulfur powder is 1:2.5 to 1:3; the temperature of the chemical vapor deposition is 820 to 850°C, and the time is 10 to 15 minutes; the substrate is any one of mica, silicon wafer or sapphire.
  • step S3 the method of transferring the MoS2 film is: using PMMA as a medium to transfer the MoS2 film on the substrate to the conductive substrate by wet etching.
  • step S4 the method for preparing the palladium chloride hydrochloric acid solution is: dissolving palladium chloride and concentrated hydrochloric acid in deionized water, and mixing them evenly to obtain the palladium chloride hydrochloric acid solution; the molar concentration ratio of the palladium chloride to the concentrated hydrochloric acid is 0.03:1 to 0.04:1.
  • the embodiments of the present disclosure further provide a MoS 2 -Pd hydrogen-sensitive material, wherein the MoS 2 -Pd hydrogen-sensitive material is prepared by the preparation method described in any embodiment of the first aspect of the present disclosure.
  • the embodiments of the present disclosure further provide an application of the MoS 2 -Pd hydrogen sensitive material in a fiber Bragg grating hydrogen sensor.
  • the MoS 2 -Pd hydrogen sensitive material is used as a hydrogen sensitive material in a fiber Bragg grating hydrogen sensor and exhibits good sensitivity and stability.
  • the present disclosure also provides a method for preparing the above fiber Bragg grating hydrogen sensor, comprising the following steps:
  • MoS2 -Pd is used as the hydrogen sensitive material
  • PMMA is used as the medium to transfer it to the processed optical fiber by wet etching. The entire process hardly causes damage to the optical fiber, so that the prepared fiber Bragg grating hydrogen sensor has a long life and good stability.
  • step 2) the rotation speed of the spin coating is 2000-3000 rpm, and the spin coating time is 45-60 s; the etching temperature is 50-70° C., and the etching time is 15-20 min.
  • metal Pd nanoparticles are deposited on the MoS2 film. Since the interaction between the Pd nanoparticles and the MoS2 film is strong, the problem of Pd easily falling off during the hydrogen absorption and release process can be overcome. In addition, the MoS2 film has a strong bonding force with the fiber Bragg grating, which can improve the structural stability of the fiber Bragg grating hydrogen sensor.
  • an electrochemical deposition method is used to firmly deposit Pd nanoparticles on the surface of the MoS2 film. Compared with the metal evaporation method and chemical reduction method commonly used in the prior art, the electrochemical deposition operation is simpler, non-destructive and low-cost.
  • the size of the Pd nanoparticles in the MoS 2 -Pd hydrogen-sensitive material can be controlled by regulating the time of electrochemical deposition, so as to meet the actual needs of the fiber Bragg grating hydrogen sensor under different working conditions.
  • the fiber Bragg grating hydrogen sensor in the embodiment of the present disclosure has a long life and good stability, and can monitor hydrogen quickly and continuously, showing good sensitivity and responsiveness.
  • FIG1 is a schematic diagram of a device for preparing MoS 2 -Pd hydrogen-sensitive material by electrochemical deposition according to an embodiment of the present disclosure
  • 1-conductive substrate loaded with MoS2 film 2-working electrode, 3-saturated calomel electrode, 4-platinum sheet counter electrode, 5-palladium chloride hydrochloric acid electroplating solution.
  • FIG. 2 is a cyclic voltammetry curve of a conductive substrate loaded with MoS 2 thin film to be deposited in a palladium chloride hydrochloric acid electroplating solution.
  • FIG3 is a structural diagram of a MoS 2 -Pd hydrogen-sensitive material in an embodiment of the present disclosure
  • 6- MoS2 thin film 7-Pd nanoparticles, 8-PMMA film, 9-Au metal film, 10-Cr metal film, 11- SiO2 , 12-Si.
  • FIG. 4 is a schematic diagram of the atomic structure of the MoS 2 -Pd hydrogen-sensitive material in an embodiment of the present disclosure.
  • FIG5 a is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in Example 1 of the present disclosure.
  • FIG5 b is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in Example 2 of the present disclosure.
  • FIG5 c is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in Example 3 of the present disclosure.
  • FIG5 d is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in Example 4 of the present disclosure.
  • FIG. 6 is a graph showing the relationship between the diameter of Pd nanoparticles and the deposition time in Examples 1-4 of the present disclosure.
  • FIG. 7 is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in Comparative Example 2.
  • FIG8 is a response curve diagram of the fiber Bragg grating hydrogen sensor prepared in Experimental Example 1 of the present disclosure to 1% concentration of hydrogen.
  • FIG. 9 is a response curve diagram of the fiber Bragg grating hydrogen sensor prepared in Experimental Example 2 of the present disclosure to 1% concentration of hydrogen.
  • an embodiment of the present disclosure provides a method for preparing a MoS 2 -Pd hydrogen-sensitive material, comprising steps S1 to S5.
  • Pd nanoparticles are loaded on the MoS2 film by adopting an electrochemical deposition method.
  • the MoS2 film has a large specific surface area and has various types of defects on its surface, including point defects (vacancies and substitutions), dislocations and grain boundaries, which can serve as active sites for the deposition of Pd2 + , so that Pd2 + can be firmly deposited at the active sites on the surface of MoS2 and reduced to Pd nanoparticles.
  • the Pd nanoparticles are firmly loaded on the MoS2 film, which enhances the interaction between the Pd nanoparticles and the MoS2 film, thereby overcoming the problem that the Pd nanoparticles are easily detached during the process of hydrogen absorption and release.
  • the metal Pd precursor salt can be reduced to metal Pd nanoparticles without the need for any additional reducing agent and a high temperature environment.
  • the electrochemical deposition method is simpler to operate, and the preparation process is environmentally friendly, non-toxic, and non-destructive, and the cost is lower.
  • the method for growing a MoS2 thin film on a substrate is: using MoO3 and sulfur powder as reaction raw materials, first placing MoO3 on a substrate and placing it in a tube furnace, and then placing a quartz boat filled with sulfur powder in the tube furnace, so that the distance between the two is 15 to 20 cm; and then growing a MoS2 thin film on the substrate by chemical vapor deposition to obtain a substrate loaded with a MoS2 thin film.
  • the molar ratio of MoO 3 to sulfur powder is 1:2.5 to 1:3, non-limiting examples include: 1:2.5, 1:2.7, 1:2.8, 1:3, etc.
  • the temperature of chemical vapor deposition is 820-850° C., non-limiting examples include 820° C., 830° C., 840° C., 850° C., etc. In some embodiments, the temperature is 850° C.
  • the time is 10 to 15 minutes, non-limiting examples include: 10 minutes, 12 minutes, 15 minutes, etc. In some embodiments, it is 15 minutes.
  • the substrate is any one of mica, silicon wafer or sapphire, and in some embodiments is mica.
  • the method for preparing the conductive substrate is: firstly, coating PMMA (polymethyl methacrylate) on a partial area of the surface of the SiO 2 /Si substrate, and heating at 100° C. for 5 to 10 minutes to solidify the PMMA to form a PMMA film; then, evaporating a metal film on the entire surface of the substrate, and then immersing it in acetone at 65° C., the metal film coated on the PMMA film will fall off as the PMMA film dissolves, so that the metal film is retained only on the residual area of the surface of the SiO 2 /Si substrate, and the conductive substrate is obtained.
  • PMMA polymethyl methacrylate
  • the vapor deposition area of the metal film accounts for 30% to 50% of the surface area of the SiO 2 /Si substrate.
  • the metal film is a Cr/Au metal film or a Ti/Au metal film, and in some embodiments, is a Cr/Au metal film.
  • the thickness ratio of the Cr metal film to the Au metal film is 1:10; and the thickness of the Cr metal film is 6-10 nm, non-limiting examples include: 6 nm, 8 nm, 10 nm, etc. In some embodiments, it is 10 nm; the thickness of the Au metal film is 60-100 nm, non-limiting examples include: 60 nm, 70 nm, 80 nm, 100 nm, etc. In some embodiments, it is 100 nm.
  • the thickness ratio of the Ti metal film to the Au metal film is 1:10; and the thickness of the Ti metal film is 6 to 10 nm, non-limiting examples include: 6 nm, 8 nm, 10 nm, etc. In some embodiments, it is 10 nm.
  • the thickness of the Au metal film is 60 to 100 nm, non-limiting examples include: 60 nm, 70 nm, 80 nm, 100 nm, etc., and in some embodiments, it is 100 nm.
  • the method for transferring the MoS2 film is: spin coating a drop of PMMA on the surface of the substrate loaded with the MoS2 film obtained in step S1, and heating at 100°C for 5 to 10 minutes to solidify the PMMA to form a PMMA film; then immersing it in deionized water, and using the surface tension of water to separate the PMMA film with the MoS2 film adhered to it from the substrate; then attaching the PMMA film with the MoS2 film to the conductive substrate obtained in step S2, and drying it so that the PMMA film with the MoS2 film adhered to it is tightly attached to the conductive substrate; finally, immersing it in a hot acetone solution at 65°C for 15 to 20 minutes to dissolve and fall off the PMMA film on the surface of the MoS2 film, and then washing it with deionized water and isopropanol in turn, and blowing it dry with nitrogen to obtain a conductive substrate with the MoS2 film loaded on the surface.
  • the spin coating speed is 2000-3000 rpm, non-limiting examples include: 2000 rpm, 2500 rpm, 2800 rpm, 3000 rpm, etc.; the spin coating time is 45-60 s, non-limiting examples include: 45 s, 50 s, 55 s, 60 s, etc.
  • step S4 the method for preparing the palladium chloride hydrochloric acid solution is: dissolving palladium chloride and concentrated hydrochloric acid in deionized water, and mixing them evenly to obtain the palladium chloride hydrochloric acid solution.
  • the molar concentration ratio of palladium chloride to concentrated hydrochloric acid is 0.03:1 to 0.04:1, non-limiting examples include 0.03:1, 0.035:1, 0.04:1, etc.
  • step S5 the constant potential is -0.20 V vs SCE, and the time of electrochemical deposition is 5 to 30 s, non-limiting examples include 5 s, 10 s, 18 s, 20 s, 25 s, 30 s, etc.; in some embodiments, it is 10 to 15 s, non-limiting examples include 10 s, 12 s, 15 s, etc.
  • Pd nanoparticles are deposited on the MoS2 film by an electrochemical deposition method, and the size of the Pd nanoparticles can be controlled by regulating the deposition time so that the actual needs of the fiber Bragg grating hydrogen sensor under different working conditions can be met.
  • This method is more flexible and simple, has a wider range of applications, and is more adaptable.
  • step S5 is to connect a conventional three-electrode system with an electrochemical workstation CHI660E for electrochemical deposition (as shown in FIG. 1 ), specifically: A saturated calomel electrode (SCE) is used as a reference electrode, a platinum sheet is used as a counter electrode, and a conductive clamp holding the conductive substrate with a surface-loaded MoS2 film obtained in step (3) is used as a working electrode; the electroplating solution uses a prepared palladium chloride hydrochloric acid solution, and it is necessary to keep a distance of 3 mm between the solution interface and the clamp to prevent the electroplating solution from seeping into the clamp.
  • SCE saturated calomel electrode
  • platinum sheet is used as a counter electrode
  • a conductive clamp holding the conductive substrate with a surface-loaded MoS2 film obtained in step (3) is used as a working electrode
  • the electroplating solution uses a prepared palladium chloride hydrochloric acid solution, and it is necessary to keep a distance of 3 mm between the
  • the deposition mode adopts constant potential deposition, and selects the appropriate deposition potential according to the potential corresponding to the position of the Pd reduction peak in the cyclic voltammetry test curve.
  • the cyclic voltammetry test is performed at a scan rate of 10mV/s, and the scan range is 0.30 to -0.45V vs SCE.
  • the cyclic voltammetry curve tends to be stable, and the potential corresponding to the position of the Pd reduction peak in the curve is approximately -0.10 to -0.20V vs SCE.
  • the inventors found that selecting a relatively negative potential can increase the nucleation density of Pd. Therefore, the deposition potential of Pd is limited to -0.20V vs SCE in the disclosed embodiment.
  • step (5) loading Pd nanoparticles on the conductive substrate with MoS2 thin film on the surface by electrochemical deposition involves an electrochemical reduction process:
  • Pd 2+ in the plating solution receives electrons and is reduced to Pd nanoparticles.
  • MoS2 is another semiconductor material that has attracted much attention after graphene, and has excellent physical and chemical properties.
  • the MoS2 film prepared in the disclosed embodiment has a large specific surface area, and there are various types of defects on its surface, including point defects (vacancies and substitutions), dislocations and grain boundaries, which can serve as deposition active sites for Pd2 + in the electroplating solution; at the same time, since the electron distribution near the defects shows obvious localized characteristics, there is a high density of electron aggregation near the vacancies, so that Pd2 + can be preferentially reduced at the defect sites, nucleate and grow to obtain Pd nanoparticles, thereby increasing the interaction between Pd nanoparticles and MoS2 film, thereby overcoming the problem that Pd nanoparticles are easy to fall off during hydrogen absorption and release.
  • Pd nanoparticles have a larger specific surface area.
  • hydrogen can be adsorbed onto the surface of Pd nanoparticles from all directions and then diffuse inward, increasing the contact area between gas molecules and Pd and shortening the time of hydrogen adsorption-permeation-diffusion, thereby improving the response speed of the hydrogen sensor.
  • the embodiment of the present disclosure also provides a MoS2 -Pd hydrogen-sensitive material, which is prepared by the above preparation method, and its macroscopic structure diagram and atomic structure schematic diagram are shown in Figure 3 and Figure 4 respectively.
  • the interaction between the metal Pd nanoparticles and the MoS2 film is stronger, which can overcome the problem of easy shedding of Pd during hydrogen absorption and release.
  • the disclosed embodiments further provide an application of the MoS 2 -Pd hydrogen sensitive material in a fiber Bragg grating hydrogen sensor.
  • the MoS 2 -Pd hydrogen sensitive material is used as a hydrogen sensitive material in a fiber Bragg grating hydrogen sensor and exhibits good sensitivity and responsiveness.
  • the present disclosure also provides a method for preparing the above fiber Bragg grating hydrogen sensor, comprising the following steps:
  • MoS2 -Pd is used as the hydrogen-sensitive material
  • PMMA is used as the medium to transfer it to the processed optical fiber by wet etching. The entire process hardly causes damage to the optical fiber, so that the prepared fiber Bragg grating hydrogen sensor has a long service life, good stability, and can quickly and continuously monitor hydrogen.
  • the spin coating speed is 2000-3000 rpm, non-limiting examples include: 2000 rpm, 2500 rpm, 2800 rpm, 3000 rpm, etc.; the spin coating time is 45-60 s, non-limiting examples include: 45 s, 50 s, 55 s, 60 s, etc.
  • the etching temperature is 50-70°C, non-limiting examples include: 50°C, 75°C, 50°C, 70°C, etc.; the etching time is 15-20 min, non-limiting examples include: 15 min, 18 min, 20 min, etc.
  • This embodiment provides a method for preparing a MoS 2 -Pd hydrogen-sensitive material, comprising the following steps:
  • PMMA polymethyl methacrylate
  • PMMA polymethyl methacrylate
  • a Cr/Au (10nm/100nm) metal film was thermally evaporated on the entire substrate surface and then immersed in 65°C acetone to coat the Cr/Au metal film on the PMMA film.
  • the metal film will fall off as the PMMA film dissolves, leaving only half of the area on the surface of the SiO 2 /Si substrate coated with the Cr/Au metal film, thus obtaining a conductive substrate;
  • a drop of PMMA is spin-coated on the surface of the mica substrate loaded with MoS2 film obtained in step S1, and heated at 100°C for 10 minutes to solidify PMMA to form a PMMA film; then immersed in deionized water, and the PMMA film with MoS2 film adhered to it is separated from the mica substrate by the surface tension of water; then the PMMA film with MoS2 film adhered to it is attached to the conductive substrate obtained in step S2, and dried, and after the water between the two evaporates, the PMMA film with MoS2 film adhered to it is tightly attached to the conductive substrate due to the van der Waals force between molecules; finally, it is immersed in a hot acetone solution at 65°C for 15 minutes, so that the PMMA film on the surface of the MoS2 film is dissolved and falls off, and then it is washed with deionized water and isopropanol in turn, and blown dry with nitrogen to obtain a conductive substrate with MoS2 film loaded on the surface;
  • the conductive substrate with the MoS 2 thin film loaded on the surface obtained in step S3 is immersed in a plating solution, and electrochemical deposition is performed at a constant potential of -0.20 V vs SCE. After deposition for 5 seconds, the substrate is immersed in deionized water to remove the residual plating solution, thereby obtaining a MoS 2 -Pd hydrogen-sensitive material.
  • FIG. 5 a it is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in this embodiment. It can be seen from the figure that the diameter of the Pd nanoparticles deposited on the MoS 2 film in this embodiment is about 2 nm.
  • the preparation process of the MoS 2 -Pd hydrogen-sensitive material in this embodiment is similar to that of the MoS 2 -Pd hydrogen-sensitive material in Example 1, with the only difference being that in this embodiment, the deposition time in step S5 is 10 s.
  • FIG. 5 b it is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in this embodiment. It can be seen from the figure that the diameter of the Pd nanoparticles deposited on the MoS 2 film in this embodiment is about 9 nm.
  • the preparation process of the MoS 2 -Pd hydrogen-sensitive material in this embodiment is similar to that of the MoS 2 -Pd hydrogen-sensitive material in Embodiment 1, with the only difference being that in this embodiment, the deposition time in step S5 is 15 s.
  • FIG. 5 c it is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in this embodiment. It can be seen from the figure that the diameter of the Pd nanoparticles deposited on the MoS 2 film in this embodiment is about 16 nm.
  • the preparation process of the MoS 2 -Pd hydrogen-sensitive material in this embodiment is similar to that of the MoS 2 -Pd hydrogen-sensitive material in Example 1, with the only difference being that in this embodiment, the deposition time in step S5 is 30 seconds.
  • FIG. 5 d it is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in this embodiment. It can be seen from the figure that the diameter of the Pd nanoparticles deposited on the MoS 2 film in this embodiment is about 36 nm.
  • Figure 6 is a relationship diagram between the diameter size of Pd nanoparticles in the MoS2 -Pd hydrogen-sensitive material prepared in Examples 1-4 of the present disclosure and the deposition time. It can be seen from the figure that the diameter size of the Pd nanoparticles is approximately linearly related to the deposition time. Therefore, the size of the Pd nanoparticles in the MoS2 -Pd hydrogen-sensitive material can be flexibly controlled by adjusting the deposition time to meet the actual needs of the hydrogen sensor under different working conditions.
  • the preparation process of the MoS 2 -Pd hydrogen-sensitive material of this comparative example is similar to that of the MoS 2 -Pd hydrogen-sensitive material of Example 4, except that: the preparation method of this comparative example does not include step S4, and in step S5 of this comparative example, a Pd metal film of about 36 nm is sputtered on the MoS 2 film by magnetron sputtering.
  • the preparation process of the MoS 2 -Pd hydrogen-sensitive material in this comparative example is similar to that of the MoS 2 -Pd hydrogen-sensitive material in Example 4, except that in this comparative example, in step S5 , electrochemical deposition is performed at a constant potential of ⁇ 0.10 V vs SCE.
  • FIG. 7 it is an atomic force microscope image of the MoS 2 -Pd hydrogen-sensitive material prepared in this comparative example. It can be seen from the figure that in the MoS 2 -Pd hydrogen-sensitive material prepared in this comparative example, the diameter of the Pd nanoparticles deposited on the MoS 2 film is about 10 nm.
  • Example 4 By comparing Example 4 with Comparative Example 2, it can be seen that the same electrochemical deposition method is used with a deposition time of 30 seconds, but the results show that in Example 4, electrochemical deposition is performed at a constant potential of -0.20 V vs SCE, and the diameter of the Pd nanoparticles in the prepared MoS 2 -Pd hydrogen-sensitive material is about 36 nm, and the nucleation density is large; while in Comparative Example 2, electrochemical deposition is performed at a constant potential of -0.10 V vs SCE, and the diameter of the Pd nanoparticles in the prepared MoS 2 -Pd hydrogen-sensitive material is only about 10 nm, and the nucleation density is relatively low. Therefore, it is further explained that the embodiment of the present disclosure uses electrochemical deposition at a constant potential of -0.20 V vs SCE to increase the nucleation density of Pd nanoparticles.
  • the MoS 2 -Pd hydrogen-sensitive material prepared in Example 4 was selected as the hydrogen-sensitive material of the fiber Bragg grating hydrogen sensor to prepare the fiber Bragg grating hydrogen sensor.
  • the preparation method of the fiber grating hydrogen sensor comprises the following steps:
  • the MoS 2 -Pd hydrogen-sensitive material prepared in Comparative Example 1 was selected as the hydrogen-sensitive material of the fiber Bragg grating hydrogen sensor to prepare the fiber Bragg grating hydrogen sensor.
  • the preparation method of the fiber Bragg grating hydrogen sensor was the same as that in Experimental Example 1.
  • the wavelength drift is 80pm
  • the sensor sensitivity is 80pm/%
  • the sensor response time and recovery time are 80s and 110s respectively
  • the wavelength drift is 45pm
  • the sensor sensitivity is 45pm/%
  • the sensor response time and recovery time are 100s and 140s respectively.
  • the wavelength fluctuates greatly and the sensor performance is attenuated.
  • the terms “one embodiment”, “some embodiments”, “examples”, “specific examples”, or “some examples” and the like mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present disclosure.
  • the schematic representations of the above terms do not necessarily refer to the same embodiment or example.
  • the described specific features, structures, materials or characteristics may be combined in any one or more embodiments or examples in a suitable manner.
  • those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, unless they are contradictory.

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Abstract

提供了一种MoS2-Pd氢敏材料及其制备方法，其制备方法包括如下步骤：在基体上生长MoS2薄膜；制备导电基底；将基体上的MoS2薄膜转移至导电基底上，得到负载有MoS2薄膜的导电基底；配制氯化钯盐酸溶液作为电镀液；将负载有MoS2薄膜的导电基底浸入电镀液中，在恒电位下进行电化学沉积后，再浸入去离子水中去除残留电镀液，即得所述MoS2-Pd氢敏材料。

Description

一种MoS2-Pd氢敏材料及其制备方法
相关申请的交叉引用
本申请要求在2023年05月15日在中国提交的中国专利申请号202310542209X的优先权，其全部内容通过引用并入本文。
技术领域
本公开属于氢气传感器技术领域，具体涉及一种MoS2-Pd氢敏材料及其制备方法。
背景技术
近年来，化石燃料不断枯竭，并且燃烧带来严重的环境污染问题。氢能具有分布广泛、清洁可再生、能量密度大和应用面广等优点，被认为是一种替代化石燃料的理想能源。然而，氢气是一种无色无味的可燃性气体，具有较低的着火能，遇到明火或电流，极易发生爆炸，同时在生产、储存和运输过程中容易发生泄漏，存在严重的安全隐患。因此，对氢气进行及时、精准、灵敏地检测具有十分重要的意义。
光纤光栅型氢气传感器具有体积小、寿命长、本质安全、抗电磁干扰、灵敏度高等优点，适合在易燃、易爆等环境中工作，目前已经成为氢检测技术的研究热点。贵金属钯(Pd)对氢气具有特异选择性和可逆吸附性，因此被广泛用于光纤光栅氢气传感器中的氢敏材料。然而，Pd在吸氢后形成Pd的氢化物存在α相和β相，α相和β相存在较大的晶格膨胀系数差异，会导致光纤光栅传感器常用的Pd膜氢敏材料在多次吸氢、释氢循环后存在开裂、脱落等问题，降低传感器的性能和使用寿命。因此，需要研发新型氢敏材料，以克服钯膜氢脆易脱落问题，提高氢气传感器性能。
发明内容
本公开实施例旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本公开实施例提出一种MoS2-Pd氢敏材料及其制备方法。
本公开实施例一方面提出一种MoS2-Pd氢敏材料的制备方法，包括如下步骤：
S1，采用化学气相沉积法在基体上生长MoS2薄膜，得到负载有所述MoS2薄膜的基体；
S2，制备导电基底；
S3，将所述基体上的所述MoS2薄膜转移至所述导电基底上，得到负载有所述MoS2薄膜的导电基底；
S4，配制氯化钯盐酸溶液作为电镀液；
S5，将所述负载有所述MoS2薄膜的导电基底浸入所述电镀液中，在恒电位下进行电化学沉积后，再浸入去离子水中去除残留电镀液，制得所述MoS2-Pd氢敏材料；
其中，所述步骤S2中，制备所述导电基底的方法是：在SiO2/Si基底表面蒸镀金属膜，得到所述导电基底；所述金属膜的蒸镀面积占所述SiO2/Si基底的表面积的30％～50％；所述金属膜为Cr/Au金属膜或Ti/Au金属膜；所述Cr/Au金属膜中，Cr金属膜与Au金属膜的厚度比为1:10；且所述Cr金属膜的厚度为6～10nm；所述Au金属膜的厚度为60～100nm；所述Ti/Au金属膜中，Ti金属膜与Au金属膜的厚度比为1:10；且所述Ti金属膜的厚度为6～10nm；所述Au金属膜的厚度为60～100nm；
所述步骤S5中，所述恒电位为-0.20V vs SCE，所述电化学沉积的时间为5～30s。
本公开实施例中，通过采用电化学沉积法在MoS2薄膜上沉积Pd纳米颗粒，由于MoS2薄膜比表面积大，且表面存在各种类型缺陷，包括点缺陷(空位和替代)、位错和晶界等，可作为Pd2+的沉积活性位点，进而使得电镀液中的Pd2+可以牢固的沉积在MoS2表面的活性位点处并在恒电位下被还原为Pd纳米颗粒。由于Pd纳米颗粒与MoS2薄膜之间的作用力较强，从而可以克服Pd纳米颗粒在吸氢、释氢过程中易脱落的问题；且通过电化学沉积法沉积Pd纳米颗粒，操作更加简便，且整个制备过程绿色无污染、无损、成本低廉。
在本公开的一些实施例中，所述步骤S1中，所述在基体上生长MoS2薄膜的方法是：以MoO3和硫粉为反应原料，通过化学气相沉积法在所述基体上生长所述MoS2薄膜，得到所述负载有所述MoS2薄膜的基体；所述MoO3与所述硫粉的摩尔比为1:2.5～1:3；所述化学气相沉积的温度为820～850℃，时间为10～15min；所述基体为云母、硅片或蓝宝石中的任一种。
在本公开的一些实施例中，所述步骤S3中，转移所述MoS2薄膜的方法是：以PMMA为媒介通过湿法刻蚀的方式将所述基体上的所述MoS2薄膜转移至所述导电基底上。
在本公开的一些实施例中，所述步骤S4中，所述配制氯化钯盐酸溶液的方法是：将氯化钯和浓盐酸溶于去离子水中，混合均匀后获得所述氯化钯盐酸溶液；所述氯化钯与所述浓盐酸的摩尔浓度比为0.03:1～0.04:1。
本公开实施例另一方面还提出一种MoS2-Pd氢敏材料，所述MoS2-Pd氢敏材料由本公开第一方面任一实施例所述制备方法制备得到。
前述针对MoS2-Pd氢敏材料的制备方法所描述的特征和优点，同样适用于MoS2-Pd氢敏材料，在此不再赘述。
本公开实施例又一方面还提出上述MoS2-Pd氢敏材料在光纤光栅氢气传感器中的应用，所述MoS2-Pd氢敏材料用作光纤光栅氢气传感器中的氢敏材料，表现出良好的灵敏度和稳定性。
本公开实施例还提出上述光纤光栅氢气传感器的制备方法，包括如下步骤：
1)采用40wt％的氢氟酸蚀刻光纤布拉格光栅表面的光纤包层，得到预处理后的光纤；
2)在MoS2-Pd氢敏材料的表面旋涂一滴PMMA，加热使所述PMMA固化形成PMMA膜；然后再浸入5wt％的NaOH溶液中，借助NaOH对SiO2/Si基底的刻蚀作用使粘有所述MoS2-Pd氢敏材料的所述PMMA膜与所述SiO2/Si基底分离，得到负载有所述MoS2-Pd氢敏材料的PMMA膜，所述MoS2-Pd氢敏材料由本公开第一方面任一实施例所述的制备方法制备得到；
3)将所述负载有所述MoS2-Pd氢敏材料的PMMA膜贴到所述预处理后的光纤上，自然晾干后，再进行加工封装，制得所述光纤光栅氢气传感器。
本公开实施例光纤光栅氢气传感器的制备方法中采用MoS2-Pd作为氢敏材料，并以PMMA为媒介通过湿法刻蚀的方式将其转移到已处理的光纤上，整个过程几乎不会对光纤造成损害，从而使得所制得的光纤光栅氢气传感器寿命高、稳定性好。
在本公开的一些实施例中，步骤2)中，所述旋涂的转速为2000～3000rpm，所述旋涂的时间为45～60s；所述刻蚀的温度为50～70℃，所述刻蚀的时间为15～20min。
本公开具有如下优点和有益效果：
(1)本公开实施例中在MoS2薄膜上沉积金属Pd纳米颗粒，由于Pd纳米颗粒与MoS2薄膜之间作用力强，从而可以克服Pd在吸氢、释氢过程中的易脱落问题，且MoS2薄膜与光纤光栅结合力较强，可以提高光纤光栅氢气传感器的结构稳定性。
(2)本公开实施例中采用电化学沉积方法将Pd纳米颗粒牢固的沉积在MoS2薄膜表面，相比于已有技术中常用的金属蒸镀法、化学还原法，采用电化学沉积操作更加简便，且无损、成本低。
(3)本公开实施例中，可以通过调控电化学沉积的时间，控制MoS2-Pd氢敏材料中的Pd纳米颗粒的尺寸，以便可以满足不同工况下光纤光栅氢气传感器的实际需求。
(4)本公开实施例中的光纤光栅氢气传感器寿命高、稳定性好，且其能够快速、连续地监测氢气，表现出良好的灵敏度和响应性。
附图说明
图1为本公开实施例电化学沉积制备MoS2-Pd氢敏材料的装置示意图；
其中，1-负载MoS2薄膜的导电基底，2-工作电极，3-饱和甘汞电极，4-铂片对电极，5-氯化钯盐酸电镀液。
图2为待沉积的负载MoS2薄膜的导电基底在氯化钯盐酸电镀液中的循环伏安曲线。
图3为本公开实施例中的MoS2-Pd氢敏材料的结构图；
其中，6-MoS2薄膜，7-Pd纳米颗粒，8-PMMA膜，9-Au金属膜，10-Cr金属膜，11-SiO2，12-Si。
图4为本公开实施例中的MoS2-Pd氢敏材料的原子结构示意图。
图5a为本公开实施例1制得的MoS2-Pd氢敏材料的原子力显微镜图。
图5b为本公开实施例2制得的MoS2-Pd氢敏材料的原子力显微镜图。
图5c为本公开实施例3制得的MoS2-Pd氢敏材料的原子力显微镜图。
图5d为本公开实施例4制得的MoS2-Pd氢敏材料的原子力显微镜图。
图6为本公开实施例1-4中Pd纳米颗粒的直径大小与沉积时间的关系图。
图7为对比例2制得的MoS2-Pd氢敏材料的原子力显微镜图。
图8为本公开实验例1中制得的光纤光栅氢气传感器对1％浓度氢气的响应曲线图。
图9为本公开实验例2中制得的光纤光栅氢气传感器对1％浓度氢气的响应曲线图。
具体实施方式
为使本公开实施例的目的、技术方案和优点更加清楚，下面将对本公开实施例的技术方案进行清楚、完整的描述。显然，所描述的实施例是本公开的一部分实施例，而不是全部的实施例。基于所描述的本公开的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本公开的保护范围。
除非另作定义，本公开实施例所使用的技术术语或者科学术语应当为本公开所属领域内有一般技能的人士所理解的通常意义。
在本文中，术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。
在本文中，术语“约”、“左右”是指所列举的值的+/-10％。
在本文中，在将值描述为范围的情况下，应当理解，这种公开包括在该范围内的所有可能的子范围的公开，以及落入该范围内的具体数值，而与是否明确指出具体数值或具体子范围无关。
本公开实施例一方面提出一种MoS2-Pd氢敏材料的制备方法，包括步骤S1至S5。
S1，在基体上生长MoS2薄膜，得到负载有MoS2薄膜的基体。
S2，制备导电基底。
S3，将基体上的MoS2薄膜转移至导电基底上，得到负载有MoS2薄膜的导电基底。
S4，配制氯化钯盐酸溶液作为电镀液。
S5，将负载有MoS2薄膜的导电基底浸入电镀液中，在恒电位下进行电化学沉积后，再浸入去离子水中去除残留电镀液，制得MoS2-Pd氢敏材料。
本公开实施例中，通过采用电化学沉积法在MoS2薄膜上负载Pd纳米颗粒，一方面，MoS2薄膜比表面积大，且表面存在各种类型缺陷，包括点缺陷(空位和替代)、位错和晶界等，可作为Pd2+的沉积活性位点，使得Pd2+可以牢固的沉积在MoS2表面的活性位点处被还原为Pd纳米颗粒，Pd纳米颗粒牢固的负载于MoS2薄膜上，增强了Pd纳米颗粒与MoS2薄膜之间的作用力，从而可以克服Pd纳米颗粒在吸氢、释氢过程中易脱落的问题；另一方面，通过电化学沉积法沉积Pd纳米颗粒，无需额外加入任何还原剂，且无需高温环境，就可以将金属Pd前驱体盐还原成金属Pd纳米颗粒，与已有技术中常用的金属蒸镀法、化学还原法相比，电化学沉积法操作更加简便，制备过程环保无毒、无损，且成本更低。
在一些具体的实施例中，步骤S1中，在基体上生长MoS2薄膜的方法是：以MoO3和硫粉为反应原料，先将MoO3置于基体上并置于管式炉中，再将装有硫粉的石英舟置于管式炉中，使二者之间的距离为15～20cm；然后再通过化学气相沉积法在基体上生长MoS2薄膜，得到负载有MoS2薄膜的基体。
在一些实施例中，MoO3与硫粉的摩尔比为1:2.5～1:3，非限制性的举例如：1:2.5、1:2.7、1:2.8、1:3等。
在一些实施例中，化学气相沉积的温度为820～850℃，非限制性的举例如：820℃、830℃、840℃、850℃等。在一些实施例中为850℃。
在一些实施例中，时间为10～15min，非限制性的举例如：10min、12min、15min等。在一些实施例中为15min。
在一些实施例中，基体为云母、硅片或蓝宝石中的任一种，在一些实施例中为云母。
在一些具体的实施例中，步骤S2中，制备导电基底的方法是：首先在SiO2/Si基底表面部分区域涂覆PMMA(聚甲基丙烯酸甲酯)，并于100℃下加热5～10min，使PMMA固化形成PMMA膜；然后再在整个基底表面上蒸镀金属膜，随后再将其浸入65℃的丙酮中，涂覆有PMMA膜上的金属膜会随着PMMA膜的溶解而脱落，使得SiO2/Si基底仅表面残余区域上保留有金属膜，即得导电基底。
在一些实施例中，金属膜的蒸镀面积占SiO2/Si基底表面积的30％～50％。
在一些实施例中，金属膜为Cr/Au金属膜或Ti/Au金属膜，在一些实施例中为Cr/Au金属膜。
在一些实施例中，Cr/Au金属膜中，Cr金属膜与Au金属膜的厚度比为1:10；且Cr金属膜的厚度为6～10nm，非限制性的举例如：6nm、8nm、10nm等。在一些实施例中为10nm；Au金属膜的厚度为60～100nm，非限制性的举例如：60nm、70nm、80nm、100nm等。在一些实施例中为100nm。
Ti/Au金属膜中，Ti金属膜与Au金属膜的厚度比为1:10；且Ti金属膜的厚度为6～10nm，非限制性的举例如：6nm、8nm、10nm等。在一些实施例中为10nm。Au金属膜的厚度为60～100nm，非限制性的举例如：60nm、70nm、80nm、100nm等，在一些实施例中为100nm。
在一些具体的实施例中，步骤S3中，转移MoS2薄膜的方法是：在步骤S1所得的负载有MoS2薄膜的基体的表面旋涂一滴PMMA，并于100℃下加热5～10min，使PMMA固化形成PMMA膜；再浸入去离子水中，借助水的表面张力使粘有MoS2薄膜的PMMA膜与基体分离；然后再将粘有MoS2薄膜的PMMA膜贴到步骤S2得到的导电基底上，并进行干燥使粘有MoS2薄膜的PMMA膜与导电基底紧密贴合；最后再将其浸入65℃的热丙酮溶液中，浸泡15～20min，使得MoS2薄膜表面的PMMA膜溶解脱落，再依次采用去离子水、异丙醇进行清洗，并用氮气吹干，获得表面负载MoS2薄膜的导电基底。
在一些实施例中，旋涂的转速为2000～3000rpm，非限制性的举例如：2000rpm、2500rpm、2800rpm、3000rpm等；旋涂的时间为45～60s，非限制性的举例如：45s、50s、55s、60s等。
在一些具体的实施例中，步骤S4中，配制氯化钯盐酸溶液的方法是：将氯化钯和浓盐酸溶于去离子水中，混合均匀后获得氯化钯盐酸溶液。
在一些实施例中，氯化钯与浓盐酸的摩尔浓度比为0.03:1～0.04:1，非限制性的举例如：0.03:1、0.035:1、0.04:1等。
在一些具体的实施例中，步骤S5中，恒电位为-0.20V vs SCE，电化学沉积的时间为5～30s，非限制性的举例如：5s、10s、18s、20s、25s、30s等；在一些实施例中为10～15s，非限制性的举例如：10s、12s、15s等。
本公开实施例中，利用电化学沉积方法在MoS2薄膜上沉积Pd纳米颗粒，且通过调控沉积的时间，就可以控制Pd纳米颗粒的尺寸大小，使其可以满足不同工况下光纤光栅氢气传感器的实际需求，该方法更加灵活简便，应用范围更广，适应性更强。
本公开实施例MoS2-Pd氢敏材料的制备方法中，步骤S5中是通过将传统的三电极体系与电化学工作站CHI660E相连接，用于进行电化学沉积(如图1所示)，具体地：以 饱和甘汞电极(SCE)作为参比电极，铂片作为对电极，导电夹具夹持着步骤(3)制得的表面负载MoS2薄膜的导电基底作为工作电极；电镀液采用配制好的氯化钯盐酸溶液，需要注意溶液界面与夹具保持3mm距离，避免电镀液浸入夹具。
沉积模式采用恒电位沉积，并根据循环伏安测试曲线中Pd还原峰位置所对应的电位来选择合适的沉积电位，具体地：以10mV/s的扫描速率进行循环伏安测试，扫描范围为0.30～-0.45V vs SCE。如图2所示，循环扫描三次后，循环伏安曲线趋于稳定，曲线中出现Pd还原峰位置对应的电位大致为-0.10～-0.20V vs SCE。发明人发现，选择相对负的电位，可以提高Pd的成核密度，因此，本公开实施例将Pd的沉积电位限定为-0.20V vs SCE。
步骤(5)中，在表面负载MoS2薄膜的导电基底上通过电化学沉积负载Pd纳米颗粒涉及电化学还原过程：
通过施加低于Pd2+(0.915V vs SHE)还原电位的沉积电位(-0.20V vs SCE)，致使电镀液中的Pd2+得到电子，被还原为Pd纳米颗粒。
MoS2作为最具代表性的新兴二维层状材料之一，是继石墨烯之后又一备受关注的半导体材料，具有优异的物理化学性质。本公开实施例所制得的MoS2薄膜比表面积大，且其表面存在各种类型缺陷，包括点缺陷(空位和替代)、位错和晶界等，可以充当电镀液中Pd2+的沉积活性位点；同时，由于缺陷附近的电子分布呈现明显的局域化特点，空位附近有高密度的电子聚集，使得Pd2+可以在缺陷位点处优先被还原，成核、生长，得到Pd纳米颗粒，因此，提高了Pd纳米颗粒与MoS2薄膜之间的作用力，进而可以克服Pd纳米颗粒在吸氢、释氢过程中易脱落的问题。此外，与金属Pd膜相比，Pd纳米颗粒具有更大的比表面积，用于氢气传感器时，氢气可以从各个方向吸附到Pd纳米颗粒表面进而向内部扩散，提高了气体分子与Pd的接触面积，缩短了氢气吸附-渗透-扩散的时间，从而可以提高氢气传感器的响应速度。
本公开实施例另一方面还提出一种MoS2-Pd氢敏材料，该氢敏材料由上述制备方法制备得到，其宏观结构图和原子结构示意图分别如图3和图4所示。本公开实施例MoS2-Pd氢敏材料中，金属Pd纳米颗粒与MoS2薄膜之间的作用力更强，可以克服Pd在吸氢、释氢过程中的易脱落问题。
本公开实施例又一方面还提出上述MoS2-Pd氢敏材料在光纤光栅氢气传感器中的应用，所述MoS2-Pd氢敏材料用作光纤光栅氢气传感器中的氢敏材料，表现出良好的灵敏度和响应性。
本公开实施例还提出上述光纤光栅氢气传感器的制备方法，包括如下步骤：
1)采用40wt％的氢氟酸蚀刻光纤布拉格光栅表面的光纤包层，得到预处理后的光纤；
2)在MoS2-Pd氢敏材料的表面旋涂一滴PMMA，并于100℃下加热5～10min，使PMMA固化形成PMMA膜；然后再浸入5wt％的NaOH溶液中，借助NaOH对SiO2/Si基底的刻蚀作用使粘有MoS2-Pd氢敏材料的PMMA膜与SiO2/Si基底分离，得到负载有MoS2-Pd氢敏材料的PMMA膜；
3)将负载有MoS2-Pd氢敏材料的PMMA膜贴到预处理后的光纤上，自然晾干后，再进行加工封装，制得所述光纤光栅氢气传感器。
本公开实施例光纤光栅氢气传感器的制备方法中采用MoS2-Pd作为氢敏材料，并以PMMA为媒介通过湿法刻蚀的方式将其转移到已处理的光纤上，整个过程几乎不会对光纤造成损害，从而使得所制得的光纤光栅氢气传感器寿命高、稳定性好，且能够快速、连续地监测氢气。
在一些具体的实施例中，步骤2)中，旋涂的转速为2000～3000rpm，非限制性的举例如：2000rpm、2500rpm、2800rpm、3000rpm等；旋涂的时间为45～60s，非限制性的举例如：45s、50s、55s、60s等。
在一些具体的实施例中，步骤2)中，刻蚀的温度为50～70℃，非限制性的举例如：50℃、75℃、50℃、70℃等；刻蚀的时间为15～20min，非限制性的举例如：15min、18min、20min等。
下面结合具体实施例对本公开技术方案作进一步详细说明，下列实施例中使用本领域常规的仪器设备，实施例中未注明具体条件的实验方法，为所属领域熟知的常规方法和常规条件，或按照制造厂商所建议的方法和条件。除非另有说明，以下实施例中使用的各种原料，均为常规市售产品，或者可以通过已知的方法制备得到。
实施例1
本实施例提供一种MoS2-Pd氢敏材料的制备方法，包括如下步骤：
S1，在基体上制备MoS2薄膜
将2.7g MoO3置于云母基体上并置于管式炉中，再将装有1.5g硫粉的石英舟置于管式炉中，使二者之间的距离为20cm；然后将管式炉升温至850℃，保温15min，使得MoO3与硫蒸气反应形成MoS2并沉积到云母基体上，获得负载有MoS2薄膜的云母基体；
S2，制备导电基底
在SiO2/Si基底表面一半区域涂覆PMMA(聚甲基丙烯酸甲酯)，并于100℃下加热10min，使PMMA固化形成PMMA膜；然后再在整个基底表面上热蒸镀Cr/Au(10nm/100nm)金属膜，随后再将其浸入65℃的丙酮中，涂覆有PMMA膜上的Cr/Au金 属膜会随着PMMA膜的溶解而脱落，使得SiO2/Si基底的表面上仅残留有一半区域镀有Cr/Au金属膜，即得导电基底；
S3，MoS2薄膜的转移
在步骤S1所得的负载有MoS2薄膜的云母基体的表面旋涂一滴PMMA，并于100℃下加热10min，使PMMA固化形成PMMA膜；再浸入去离子水中，借助水的表面张力使粘有MoS2薄膜的PMMA膜与云母基体分离；然后再将粘有MoS2薄膜的PMMA膜贴到步骤S2得到的导电基底上，并进行干燥，待二者之间的水分蒸发后，由于分子间的范德华作用力，使粘有MoS2薄膜的PMMA膜与导电基底紧密贴合；最后再将其浸入65℃的热丙酮溶液中，浸泡15min，使得MoS2薄膜表面的PMMA膜溶解脱落，再依次采用去离子水、异丙醇进行清洗，并用氮气吹干，获得表面负载MoS2薄膜的导电基底；
S4，配制电镀液
将0.53g的氯化钯和3.1mL 36％的浓盐酸溶解于1000mL去离子水中，混合均匀后获得氯化钯盐酸溶液，将其作为电化学沉积法制备金属Pd纳米颗粒的电镀液；
S5，电化学沉积法在MoS2薄膜上可控沉积Pd纳米颗粒
将步骤S3所得的表面负载MoS2薄膜的导电基底浸入电镀液中，在-0.20V vs SCE恒电位下进行电化学沉积，沉积5s后，再浸入去离子水中去除残留电镀液，即得MoS2-Pd氢敏材料。
如图5a所示，为本实施例制得的MoS2-Pd氢敏材料的原子力显微镜图像，由图中可以看出，本实施例MoS2薄膜上沉积的Pd纳米颗粒的直径约为2nm。
实施例2
本实施例的MoS2-Pd氢敏材料的制备过程与实施例1的MoS2-Pd氢敏材料的制备过程相似，区别仅在于：本实施例中，步骤S5中的沉积时间为10s。
如图5b所示，为本实施例制得的MoS2-Pd氢敏材料的原子力显微镜图像，由图中可以看出，本实施例MoS2薄膜上沉积的Pd纳米颗粒的直径约为9nm。
实施例3
本实施例的MoS2-Pd氢敏材料的制备过程与实施例1的MoS2-Pd氢敏材料的制备过程相似，区别仅在于：本实施例中，步骤S5中的沉积时间为15s。
如图5c所示，为本实施例制得的MoS2-Pd氢敏材料的原子力显微镜图像，由图中可以看出，本实施例MoS2薄膜上沉积的Pd纳米颗粒的直径约为16nm。
实施例4
本实施例的MoS2-Pd氢敏材料的制备过程与实施例1的MoS2-Pd氢敏材料的制备过程相似，区别仅在于：本实施例中，步骤S5中的沉积时间为30s。
如图5d所示，为本实施例制得的MoS2-Pd氢敏材料的原子力显微镜图像，由图中可以看出，本实施例MoS2薄膜上沉积的Pd纳米颗粒的直径约为36nm。
图6为本公开实施例1-4制得的MoS2-Pd氢敏材料中Pd纳米颗粒的直径大小与沉积时间的关系图，由图可知，Pd纳米颗粒的直径大小与沉积时间近似呈线性关系，因此，可以通过调节沉积时间来灵活的调控MoS2-Pd氢敏材料中Pd纳米颗粒的尺寸，从而满足不同工况下氢气传感器的实际需求。
对比例1
本对比例的MoS2-Pd氢敏材料的制备过程与实施例4的MoS2-Pd氢敏材料的制备过程相似，区别在于：本对比例的制备方法中，不包括步骤S4，且本对比例步骤S5中是采用磁控溅射的方式在MoS2薄膜上溅射36nm左右的Pd金属膜。
对比例2
本对比例的MoS2-Pd氢敏材料的制备过程与实施例4的MoS2-Pd氢敏材料的制备过程相似，区别在于：本对比例中，步骤S5中，是在-0.10V vs SCE的恒电位下进行电化学沉积。
如图7所示，为本对比例制得的MoS2-Pd氢敏材料的原子力显微镜图像，由图中可以看出，本对比例制得的MoS2-Pd氢敏材料中，MoS2薄膜上沉积的Pd纳米颗粒的直径约为10nm。
通过对比实施例4与对比例2可知，同样采用电化学沉积方法，沉积时间30s，但结果表明，实施例4中在-0.20V vs SCE恒电位下进行电化学沉积，其所制得的MoS2-Pd氢敏材料中Pd纳米颗粒的直径约为36nm，成核密度大；而对比例2中在-0.10V vs SCE恒电位下进行电化学沉积，其所制得的MoS2-Pd氢敏材料中Pd纳米颗粒的直径仅为10nm左右，成核密度较小。由此，进一步说明本公开实施例选用在-0.20V vs SCE恒电位下进行电化学沉积，可以提高Pd纳米颗粒的成核密度。
实验例1
本实验例选用实施例4中制得的MoS2-Pd氢敏材料作为光纤光栅氢气传感器的氢敏材料，制备光纤光栅氢气传感器。
该光纤光栅氢气传感器的制备方法，包括如下步骤：
1)采用40wt％的氢氟酸蚀刻光纤布拉格光栅表面的光纤包层，得到预处理后的光纤；
2)在3000rpm的转速下，在MoS2-Pd氢敏材料的表面旋涂一滴PMMA，旋涂60s，并于100℃下加热5～10min，使PMMA固化形成PMMA膜；然后再浸入5wt％的NaOH溶液中，于50℃下，借助NaOH对SiO2/Si基底的刻蚀作用使粘有MoS2-Pd氢敏材料的 PMMA膜与SiO2/Si基底分离，刻蚀15min后，得到负载有MoS2-Pd氢敏材料的PMMA膜；
3)将负载有MoS2-Pd氢敏材料的PMMA膜贴到预处理后的光纤上，自然晾干，MoS2-Pd氢敏材料表面的PMMA膜直接作为保护层不用除去；最后再进行加工封装，制得即得光纤光栅氢气传感器。
对上述制得的光纤光栅氢气传感器进行氢气检测实验：将制备好的光纤光栅氢气传感器放置在气体室中，并通入浓度为1％的氢气，用以检测上述光纤光栅氢气传感器对1％浓度氢气实时循环响应情况，测试结果如图8所示。
从图8中可以看出，当氢气浓度从0增加到1％时，波长发生明显漂移，波长漂移为105pm，传感器灵敏度为105pm/％，灵敏度较高；传感器的响应时间和恢复时间分别为25s和40s，同时波长波动小，传感器的稳定性良好。与同类型Pd基光纤光栅氢气传感器相比，传感器性能十分优异。
上述测试结果表明，本公开实施例基于MoS2-Pd氢敏材料的光纤光栅氢气传感器能够快速、连续地监测氢气，表现出良好的灵敏性、响应性和稳定性。
实验例2
本实验例选用对比例1中制得的MoS2-Pd氢敏材料作为光纤光栅氢气传感器的氢敏材料，制备光纤光栅氢气传感器，该光纤光栅氢气传感器的制备方法与实验例1中的制备方法相同。
对本实验例制得的光纤光栅氢气传感器进行氢气检测实验：将制备好的光纤光栅氢气传感器放置在气体室中，并通入浓度为1％的氢气，用以检测上述光纤光栅氢气传感器对1％浓度氢气实时循环响应情况，测试结果如图9所示。
从图9中可以看出，当氢气浓度首次从0增加到1％时，波长漂移为80pm，传感器灵敏度为80pm/％，传感器的响应时间和恢复时间分别为80s和110s；后两次实验中波长漂移为45pm，传感器灵敏度为45pm/％，传感器的响应时间和恢复时间分别为100s和140s，波长波动较大，传感器的性能衰减。
从上述结果可知，与电化学沉积方法在MoS2薄膜上沉积Pd纳米颗粒相比，通过磁控溅射的方式在MoS2薄膜上溅射Pd金属膜，由于Pd金属膜与MoS2的结合力弱于Pd纳米颗粒与MoS2的结合力，导致其与氢气反应过程中容易发生部分Pd金属膜相变，Pd金属膜脆化、脱落，进而导致光纤光栅氢气传感器灵敏度下降，多次测试下性能会衰减；且Pd金属膜与Pd纳米颗粒相比，Pd金属膜的比表面积更小，从而减少了氢气分子与Pd的接触面积，导致氢气吸附-渗透-扩散的时间更长，因此制备的光纤光栅氢气传感器具有较 长的响应时间和恢复时间；此外，与电化学沉积方法相比，磁控溅射并非无损过程，导致制备的MoS2-Pd氢敏材料质量下降。
在本公开中，术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本公开的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本公开的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本公开的限制，本领域的普通技术人员在本公开的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (8)

  1. 一种MoS2-Pd氢敏材料的制备方法，其特征在于，包括如下步骤：
    S1，采用化学气相沉积法在基体上生长MoS2薄膜，得到负载有所述MoS2薄膜的基体；
    S2，制备导电基底；
    S3，将所述基体上的所述MoS2薄膜转移至所述导电基底上，得到负载有所述MoS2薄膜的导电基底；
    S4，配制氯化钯盐酸溶液作为电镀液；
    S5，将所述负载有所述MoS2薄膜的导电基底浸入所述电镀液中，在恒电位下进行电化学沉积后，再浸入去离子水中去除残留电镀液，制得所述MoS2-Pd氢敏材料；
    其中，所述步骤S2中，制备所述导电基底的方法是：在SiO2/Si基底表面蒸镀金属膜，得到所述导电基底；所述金属膜的蒸镀面积占所述SiO2/Si基底的表面积的30％～50％；所述金属膜为Cr/Au金属膜或Ti/Au金属膜；所述Cr/Au金属膜中，Cr金属膜与Au金属膜的厚度比为1:10；且所述Cr金属膜的厚度为6～10nm；所述Au金属膜的厚度为60～100nm；所述Ti/Au金属膜中，Ti金属膜与Au金属膜的厚度比为1:10；且所述Ti金属膜的厚度为6～10nm；所述Au金属膜的厚度为60～100nm；
    所述步骤S5中，所述恒电位为-0.20V vs SCE，所述电化学沉积的时间为5～30s。
  2. 根据权利要求1所述的MoS2-Pd氢敏材料的制备方法，其特征在于，所述步骤S1中，所述在基体上生长MoS2薄膜的方法是：以MoO3和硫粉为反应原料，通过化学气相沉积法在所述基体上生长所述MoS2薄膜，得到所述负载有所述MoS2薄膜的基体；所述MoO3与所述硫粉的摩尔比为1:2.5～1:3；所述化学气相沉积的温度为820～850℃，时间为10～15min；所述基体为云母、硅片或蓝宝石中的任一种。
  3. 根据权利要求1或2所述的MoS2-Pd氢敏材料的制备方法，其特征在于，所述步骤S3中，转移所述MoS2薄膜的方法是：以PMMA为媒介通过湿法刻蚀的方式将所述基体上的所述MoS2薄膜转移至所述导电基底上。
  4. 根据权利要求1至3中任一项所述的MoS2-Pd氢敏材料的制备方法，其特征在于，所述步骤S4中，所述配制氯化钯盐酸溶液的方法是：将氯化钯和浓盐酸溶于去离子水中，混合均匀后获得所述氯化钯盐酸溶液；所述氯化钯与所述浓盐酸的摩尔浓度比为0.03:1～0.04:1。
  5. 一种MoS2-Pd氢敏材料，其特征在于，所述MoS2-Pd氢敏材料由权利要求1至4中任一项所述的制备方法制备得到。
  6. 权利要求5所述的MoS2-Pd氢敏材料在光纤光栅氢气传感器中的应用，其特征在于，所述MoS2-Pd氢敏材料用作光纤光栅氢气传感器中的氢敏材料。
  7. 一种光纤光栅氢气传感器的制备方法，其特征在于，包括如下步骤：
    1)采用40wt％的氢氟酸蚀刻光纤布拉格光栅表面的光纤包层，得到预处理后的光纤；
    2)在MoS2-Pd氢敏材料的表面旋涂一滴PMMA，加热使所述PMMA固化形成PMMA膜；然后再浸入5wt％的NaOH溶液中，借助NaOH对SiO2/Si基底的刻蚀作用使粘有所述MoS2-Pd氢敏材料的所述PMMA膜与所述SiO2/Si基底分离，得到负载有所述MoS2-Pd氢敏材料的PMMA膜，所述MoS2-Pd氢敏材料由权利要求1至4中任一项所述的制备方法制备得到；
    3)将所述负载有所述MoS2-Pd氢敏材料的PMMA膜贴到所述预处理后的光纤上，自然晾干后，再进行加工封装，制得所述光纤光栅氢气传感器。
  8. 根据权利要求7所述的光纤光栅氢气传感器的制备方法，其特征在于，步骤2)中，所述旋涂的转速为2000～3000rpm，所述旋涂的时间为45～60s；所述刻蚀的温度为50～70℃，所述刻蚀的时间为15～20min。
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