CN116288234B - MoS (MoS) 2 Pd hydrogen sensitive material and preparation method thereof - Google Patents
MoS (MoS) 2 Pd hydrogen sensitive material and preparation method thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 172
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 172
- 239000000463 material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 149
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 132
- 239000000758 substrate Substances 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 53
- 238000004070 electrodeposition Methods 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000009713 electroplating Methods 0.000 claims abstract description 22
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims description 65
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- 238000005530 etching Methods 0.000 claims description 15
- 238000004528 spin coating Methods 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
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- 239000010445 mica Substances 0.000 claims description 10
- 229910052618 mica group Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
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- 239000002105 nanoparticle Substances 0.000 abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 29
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
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- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
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- 229910052763 palladium Inorganic materials 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
Abstract
The invention discloses a MoS 2 -Pd hydrogen-sensitive material and preparation method thereof, the preparation method comprises the following steps: growth of MoS on a substrate 2 A film; preparing a conductive substrate; moS on a substrate 2 Transferring the film onto a conductive substrate to obtain a MoS-loaded film 2 A conductive substrate of the film; preparing palladium chloride hydrochloric acid solution as electroplating solution; will be loaded with MoS 2 Immersing the conductive substrate of the film into electroplating solution, performing electrochemical deposition under constant potential, and immersing into deionized water to remove residual electroplating solution to obtain the MoS 2 -Pd hydrogen sensitive material. In the invention, pd nano particles are deposited on MoS by adopting an electrochemical deposition method 2 Pd nano particles and MoS on the film 2 The acting force between the films is strong, so that the problem that Pd is easy to fall off in the hydrogen absorption and release process can be solved; and the whole preparation process is green, pollution-free and nondestructive.
Description
Technical Field
The invention belongs to the technical field of hydrogen sensors, and particularly relates to a MoS 2 Pd hydrogen sensitive material and its preparation process.
Background
In recent years, fossil fuels are continuously exhausted, and combustion brings about serious environmental pollution problems. The hydrogen energy has the advantages of wide distribution, cleanness, regeneration, high energy density, wide application range and the like, and is considered as an ideal energy source for replacing fossil fuel. However, hydrogen is colorless and odorless combustible gas, has low ignition energy, is extremely easy to explode when encountering open fire or current, and is easy to leak in the production, storage and transportation processes, so that serious potential safety hazards exist. Therefore, the method has very important significance for timely, accurately and sensitively detecting the hydrogen.
The fiber bragg grating type hydrogen sensor has the advantages of small volume, long service life, intrinsic safety, electromagnetic interference resistance, high sensitivity and the like, is suitable for working in flammable, explosive and other environments, and is currently becoming a research hotspot of hydrogen detection technology. Noble metal palladium (Pd) has specific selectivity and reversible adsorptivity to hydrogen, and thus is widely used as a hydrogen-sensitive material in fiber grating hydrogen sensors. However, the hydride of Pd formed after the Pd absorbs hydrogen has an alpha phase and a beta phase, and the alpha phase and the beta phase have larger lattice expansion coefficient difference, so that the common Pd film hydrogen-sensitive material of the fiber bragg grating sensor has the problems of cracking, falling off and the like after repeated hydrogen absorption and hydrogen release cycles, and the performance and the service life of the sensor are reduced. Therefore, a novel hydrogen-sensitive material needs to be developed to overcome the problem that palladium membranes are fragile and easy to fall off and improve the performance of the hydrogen sensor.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. For this reason, the embodiment of the invention provides a MoS 2 Pd hydrogen sensitive material and its preparation process.
One aspect of the embodiment of the invention provides a MoS 2 -a method for preparing a Pd hydrogen sensitive material, comprising the steps of:
s1, growing MoS on a substrate 2 Film, get MoS loaded 2 A substrate of the film;
s2, preparing a conductive substrate;
s3, moS on the substrate 2 Transferring the film onto the conductive substrate to obtain a loaded MoS 2 A conductive substrate of the film;
s4, preparing palladium chloride hydrochloric acid solution as electroplating solution;
s5, loading the MoS on the load 2 Immersing the conductive substrate of the film into the electroplating solution, performing electrochemical deposition under constant potential, and immersing into deionized water to remove residual electroplating solution to obtain the MoS 2 -Pd hydrogen sensitive material.
In the embodiment of the invention, the electrochemical deposition method is adopted in MoS 2 Deposition of Pd nanoparticles on thin films due to MoS 2 The specific surface area of the film is large, and various defects including point defects (vacancies and substitutes), dislocation, grain boundary and the like exist on the surface, which can be used as Pd 2+ To deposit active sites, therebySo that Pd in the electroplating solution 2+ Can be firmly deposited on MoS 2 The active sites on the surface are reduced to Pd nanoparticles at constant potential. Due to Pd nano-particles and MoS 2 The acting force between the films is strong, so that the problem that Pd nano particles are easy to fall off in the hydrogen absorption and release process can be solved; and Pd nano particles are deposited by an electrochemical deposition method, so that the operation is simpler and more convenient, and the whole preparation process is green, pollution-free, lossless and low in cost.
In some embodiments of the invention, in the step S1, moS is grown on the substrate 2 The method for the film comprises the following steps: in MoO 3 And sulfur powder as reaction raw materials, and growing MoS on a substrate by a chemical vapor deposition method 2 Film, get MoS loaded 2 A substrate of the film;
and/or the MoO 3 The molar ratio of the sulfur powder to the sulfur powder is 1:2.5-1:3;
and/or the temperature of the chemical vapor deposition is 820-850 ℃, preferably 850 ℃; the time is 10-15 min, preferably 15min;
and/or the matrix is any one of mica, silicon wafer or sapphire, preferably mica.
In some embodiments of the present invention, in the step S2, the method for preparing the conductive substrate is: in SiO 2 Evaporating a metal film on the surface of the Si substrate to obtain the conductive substrate;
and/or the vapor deposition area of the metal film occupies the SiO 2 30% -50% of the surface area of the Si substrate;
and/or the metal film is a Cr/Au metal film or a Ti/Au metal film, preferably a Cr/Au metal film;
and/or, in the Cr/Au metal film, the thickness ratio of the Cr metal film to the Au metal film is 1:10; the thickness of the Cr metal film is 6-10 nm, preferably 10nm; the thickness of the Au metal film is 60-100 nm, preferably 100nm;
and/or, in the Ti/Au metal film, the thickness ratio of the Ti metal film to the Au metal film is 1:10; the thickness of the Ti metal film is 6-10 nm, preferably 10nm; the thickness of the Au metal film is 60-100 nm, preferably 100nm.
In some embodiments of the present invention, in the step S3, moS is transferred 2 The method for the film comprises the following steps: moS on the substrate is etched by a wet method by taking PMMA as a medium 2 The film is transferred to the conductive substrate.
In some embodiments of the present invention, in the step S4, the method for preparing the palladium chloride hydrochloric acid solution is: dissolving palladium chloride and concentrated hydrochloric acid in deionized water, and uniformly mixing to obtain a palladium chloride hydrochloric acid solution;
and/or the molar concentration ratio of the palladium chloride to the concentrated hydrochloric acid is 0.03:1-0.04:1.
In some embodiments of the present invention, in the step S5, the potentiostatic voltage is-0.20V vs SCE, and the time for the electrochemical deposition is 5 to 30S, preferably 10 to 15S.
On the other hand, the embodiment of the invention also provides a MoS 2 -Pd hydrogen sensitive material, said MoS 2 The Pd hydrogen sensitive material is prepared by the preparation method.
The foregoing is directed to MoS 2 The features and advantages described for the preparation of Pd hydrogen-sensitive materials are likewise applicable to MoS 2 Pd hydrogen sensitive material, which is not described in detail herein.
In a further aspect of the embodiment of the present invention, the foregoing MoS is further provided 2 Application of Pd hydrogen-sensitive material in fiber grating hydrogen sensor, moS 2 Pd hydrogen-sensitive material is used as hydrogen-sensitive material in fiber grating hydrogen sensor, and has excellent sensitivity and stability.
The embodiment of the invention also provides a preparation method of the fiber bragg grating hydrogen sensor, which comprises the following steps:
1) Etching the fiber cladding on the surface of the fiber Bragg grating by adopting 40wt% hydrofluoric acid to obtain a pretreated fiber;
2) In MoS 2 Spin-coating a drop of PMMA on the surface of the Pd hydrogen-sensitive material, and heating to cure the PMMA to form a PMMA film; then immersing in 5wt% NaOH solution, and SiO is treated by NaOH 2 Etching of the Si substrate to adhere MoS 2 PMMA film of Pd hydrogen sensitive material and SiO 2 Separation of Si substrate to obtain a carrierMoS 2 -a PMMA film of Pd hydrogen sensitive material;
3) Will be loaded with MoS 2 And (3) attaching a PMMA film of the Pd hydrogen-sensitive material to the pretreated optical fiber, naturally airing, and then processing and packaging to obtain the fiber grating hydrogen sensor.
In the preparation method of the fiber bragg grating hydrogen sensor, moS is adopted 2 Pd is used as a hydrogen-sensitive material and is transferred onto the processed optical fiber by taking PMMA as a medium through a wet etching mode, and the optical fiber is hardly damaged in the whole process, so that the prepared fiber bragg grating hydrogen sensor has the advantages of long service life and good stability.
In some embodiments of the present invention, in step 2), the spin-coating speed is 2000-3000 rpm, and the spin-coating time is 45-60 s.
In some embodiments of the present invention, in step 2), the etching temperature is 50-70 ℃ and the etching time is 15-20 min.
The invention has the following advantages and beneficial effects:
(1) In the embodiment of the invention, moS 2 Metal Pd nano-particles are deposited on the film, and the Pd nano-particles and MoS 2 The acting force between the films is strong, thereby overcoming the problem that Pd is easy to fall off in the hydrogen absorption and release processes, and MoS 2 The film has strong binding force with the fiber grating, and can improve the structural stability of the fiber grating hydrogen sensor.
(2) In the embodiment of the invention, pd nano particles are firmly deposited on MoS by adopting an electrochemical deposition method 2 Compared with the metal evaporation method and the chemical reduction method which are commonly used in the prior art, the surface of the film is more convenient to use electrochemical deposition operation, and has no damage and low cost.
(3) In the embodiment of the invention, moS can be controlled by regulating and controlling the time of electrochemical deposition 2 The size of Pd nano particles in the Pd hydrogen sensitive material can meet the actual requirements of the fiber grating hydrogen sensor under different working conditions.
(4) The fiber bragg grating hydrogen sensor provided by the embodiment of the invention has the advantages of high service life and good stability, can be used for rapidly and continuously monitoring hydrogen, and has good sensitivity and responsiveness.
Drawings
FIG. 1 is a schematic illustration of the electrochemical deposition process for preparing MoS in accordance with an embodiment of the present invention 2 -schematic of the apparatus of Pd hydrogen sensitive material;
wherein, 1-load MoS 2 The conductive substrate of the film, a 2-working electrode, a 3-saturated calomel electrode, a 4-platinum sheet counter electrode and 5-palladium chloride hydrochloric acid electroplating solution.
FIG. 2 is a load MoS to be deposited 2 Cyclic voltammogram of the conductive substrate of the film in palladium chloride hydrochloric acid plating solution.
FIG. 3 is a MoS in an embodiment of the invention 2 -a structural diagram of a Pd hydrogen sensitive material;
wherein, 6-MoS 2 Film, 7-Pd nanoparticle, 8-PMMA film, 9-Au metal film, 10-Cr metal film, 11-SiO 2 ，12-Si。
FIG. 4 is a MoS of an embodiment of the invention 2 -atomic structural schematic of Pd hydrogen sensitive material.
FIG. 5a is a MoS obtained in example 1 of the present invention 2 Atomic force microscopy of Pd-hydrogen sensitive material.
FIG. 5b is a MoS of example 2 of the present invention 2 Atomic force microscopy of Pd-hydrogen sensitive material.
FIG. 5c shows a MoS obtained in example 3 of the present invention 2 Atomic force microscopy of Pd-hydrogen sensitive material.
FIG. 5d shows the MoS of example 4 of the present invention 2 Atomic force microscopy of Pd-hydrogen sensitive material.
FIG. 6 is a graph showing the relationship between the diameter size and the deposition time of Pd nanoparticles in examples 1 to 4 of the present invention.
FIG. 7 is a MoS obtained in comparative example 2 2 Atomic force microscopy of Pd-hydrogen sensitive material.
FIG. 8 is a graph showing the response of the fiber grating hydrogen sensor prepared in Experimental example 1 to 1% concentration hydrogen.
FIG. 9 is a graph showing the response of the fiber grating hydrogen sensor prepared in Experimental example 2 to 1% concentration hydrogen.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without creative efforts, based on the described embodiments of the present invention belong to the protection scope of the present invention.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
In this document, the term "and/or" is merely an association relation describing an associated object, meaning that there may be three relations, e.g. a and/or B, which may mean: a exists alone, A and B exist together, and B exists alone.
In this context, the terms "about", "left and right" refer to +/-10% of the recited values.
Where a value is described herein as a range, it is understood that such disclosure includes disclosure of all possible sub-ranges within the range, as well as specific values falling within the range, regardless of whether the specific value or sub-range is explicitly recited.
One aspect of the embodiment of the invention provides a MoS 2 -a method for preparing a Pd hydrogen sensitive material, comprising the steps of:
s1, growing MoS on a substrate 2 Film, get MoS loaded 2 A substrate of the film;
s2, preparing a conductive substrate;
s3, moS on the substrate 2 Transferring the film onto a conductive substrate to obtain a MoS-loaded film 2 A conductive substrate of the film;
s4, preparing palladium chloride hydrochloric acid solution as electroplating solution;
s5, loading MoS 2 Immersing the conductive substrate of the film in electroplating solution, and performing electrochemical deposition under constant potentialImmersing in deionized water to remove residual electroplating solution to obtain MoS 2 -Pd hydrogen sensitive material.
In the embodiment of the invention, the electrochemical deposition method is adopted in MoS 2 Pd nano particles are loaded on the film, on one hand, moS 2 The specific surface area of the film is large, and various defects including point defects (vacancies and substitutes), dislocation, grain boundary and the like exist on the surface, which can be used as Pd 2+ Such that Pd is deposited on the active sites of 2+ Can be firmly deposited on MoS 2 The active site of the surface is reduced into Pd nano-particles, and the Pd nano-particles are firmly supported on MoS 2 On the film, pd nano particles and MoS are enhanced 2 The acting force between the films can overcome the problem that Pd nano particles are easy to fall off in the hydrogen absorption and release process; on the other hand, the Pd nano particles are deposited by the electrochemical deposition method, any reducing agent is not required to be added additionally, and the metal Pd precursor salt can be reduced into the metal Pd nano particles without high-temperature environment.
In some specific embodiments, in step S1, moS is grown on a substrate 2 The method for the film comprises the following steps: in MoO 3 Mixing with sulfur powder as reaction material, moO 3 Placing the quartz boat on a substrate and placing the quartz boat in a tube furnace, and placing the quartz boat in the tube furnace, wherein the distance between the quartz boat and the tube furnace is 15-20 cm; then growing MoS on the substrate by chemical vapor deposition 2 Film, get MoS loaded 2 A substrate of the film;
further, moO 3 The molar ratio of the sulfur powder to the sulfur powder is 1:2.5-1:3, and the following non-limiting examples are: 1:2.5, 1:2.7, 1:2.8, 1:3, etc.;
and/or, the temperature of the chemical vapor deposition is 820-850 ℃, such as, without limitation: 820 ℃, 830 ℃, 840 ℃, 850 ℃ and the like, preferably 850 ℃; the time is 10-15 min, such as, without limitation: 10min, 12min, 15min, etc., preferably 15min;
and/or the matrix is any one of mica, silicon wafer or sapphire, preferably mica.
In some specific embodiments, in step S2, the method of preparing the conductive substrate is: first at SiO 2 Coating PMMA (polymethyl methacrylate) on a partial area of the surface of the Si substrate, and heating at 100 ℃ for 5-10 min to cure the PMMA to form a PMMA film; then evaporating a metal film on the whole substrate surface, immersing the metal film in acetone at 65 ℃, and peeling the metal film coated with the PMMA film along with the dissolution of the PMMA film to enable the SiO to be formed 2 The metal film is reserved on the surface residual area of the Si substrate, and the conductive substrate is obtained;
further, the vapor deposition area of the metal film occupies SiO 2 30% -50% of the surface area of the Si substrate;
and/or the metal film is a Cr/Au metal film or a Ti/Au metal film, preferably a Cr/Au metal film;
preferably, 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 6-10 nm, such as, but not limited to: 6nm, 8nm, 10nm, etc., preferably 10nm; the thickness of the Au metal film is 60-100 nm, such as, but not limited to: 60nm, 70nm, 80nm, 100nm, etc., preferably 100nm;
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 6-10 nm, such as, but not limited to: 6nm, 8nm, 10nm, etc., preferably 10nm; the thickness of the Au metal film is 60-100 nm, such as, but not limited to: 60nm, 70nm, 80nm, 100nm, etc., preferably 100nm.
In some specific embodiments, in step S3, moS is transferred 2 The method for the film comprises the following steps: the load obtained in step S1 is MoS 2 Spin-coating a drop of PMMA on the surface of the matrix of the film, and heating at 100 ℃ for 5-10 min to solidify the PMMA to form a PMMA film; immersing in deionized water, sticking MoS by water surface tension 2 Separating the PMMA film of the thin film from the substrate; then sticking MoS 2 Attaching PMMA film of the film to the conductive substrate obtained in step S2, and drying to adhere MoS 2 The PMMA film of the film is tightly attached to the conductive substrate; finally, the mixture is immersed into hot acetone solution at 65 DEG CSoaking in the solution for 15-20 min to enable MoS 2 Dissolving and falling PMMA film on the surface of the film, cleaning by adopting deionized water and isopropanol in sequence, and drying by using nitrogen to obtain surface-loaded MoS 2 A conductive substrate of the film;
further, the spin coating is performed at a rotational speed of 2000 to 3000rpm, such as, but not limited to: 2000rpm, 2500rpm, 2800rpm, 3000rpm, etc.; the spin coating time is 45-60 s, such as, but not limited to: 45s, 50s, 55s, 60s, etc.
In some specific embodiments, in step S4, the method for preparing the palladium chloride hydrochloric acid solution is: dissolving palladium chloride and concentrated hydrochloric acid in deionized water, and uniformly mixing to obtain a palladium chloride hydrochloric acid solution;
further, the molar concentration ratio of palladium chloride to concentrated hydrochloric acid is 0.03:1 to 0.04:1, such as, without limitation: 0.03:1, 0.035:1, 0.04:1, etc.
In some specific embodiments, in step S5, the constant potential is-0.20V vs SCE, and the electrochemical deposition time is 5-30S, such as, but not limited to: 5s, 10s, 18s, 20s, 25s, 30s, etc.; preferably 10 to 15s, such as, without limitation: 10s, 12s, 15s, etc.
In the embodiment of the invention, an electrochemical deposition method is utilized in MoS 2 The Pd nano particles are deposited on the film, and the size of the Pd nano particles can be controlled by regulating and controlling the deposition time, so that the method can meet the actual demands of the fiber bragg grating hydrogen sensor under different working conditions, and is more flexible, simpler and more convenient, wider in application range and stronger in adaptability.
Embodiment of the invention MoS 2 In the process for the preparation of Pd-hydrogen-sensitive materials, step S5 is carried out by connecting a conventional three-electrode system to an electrochemical workstation CHI660E for electrochemical deposition (as shown in fig. 1), in particular: using a Saturated Calomel Electrode (SCE) as a reference electrode, using a platinum sheet as a counter electrode, and clamping the surface load MoS prepared in the step (3) by a conductive clamp 2 The conductive substrate of the film is used as a working electrode; the electroplating solution adopts the prepared palladium chloride hydrochloric acid solution, and the distance between the solution interface and the clamp is required to be kept 3mm, so that the electroplating solution is prevented from immersing into the clamp.
The deposition mode adopts potentiostatic deposition, and proper deposition potential is selected according to the potential corresponding to the Pd reduction peak position in the cyclic voltammetry test curve, in particular: cyclic voltammetry was performed at a scan rate of 10mV/s, with a scan range of 0.30 to-0.45V vs SCE. As shown in FIG. 2, after three times of cyclic scanning, the cyclic voltammetry curve is stable, and the potential corresponding to the position of Pd reduction peak in the curve is approximately-0.10 to-0.20V vs SCE. The inventors found that the nucleation density of Pd can be increased by selecting a relatively negative potential, and thus, the present embodiment limits the deposition potential of Pd to-0.20V vs SCE.
In step (5), moS is loaded on the surface 2 Loading Pd nanoparticles on a conductive substrate of a thin film by electrochemical deposition involves an electrochemical reduction process:
by applying less than Pd 2+ (0.915V vs SHE) deposition potential of reduction potential (-0.20V vs SCE), so that Pd in the electroplating solution 2+ Electrons are obtained and reduced to Pd nanoparticles.
MoS 2 One of the most representative emerging two-dimensional layered materials is a semiconductor material of further interest following graphene, with excellent physicochemical properties. MoS prepared by the embodiment of the invention 2 The thin film has large specific surface area, and various defects including point defects (vacancies and substitutes), dislocation, grain boundaries and the like exist on the surface, and can be used as Pd in the electroplating solution 2+ Is used for depositing active sites; meanwhile, because the electron distribution near the defects presents obvious localization characteristics, electrons with high density are gathered near the vacancies, so that Pd 2+ Can be reduced, nucleated and grown at the defect site preferentially to obtain Pd nano-particles, thus improving the Pd nano-particles and MoS 2 The acting force between the films can further overcome the problem that Pd nano particles are easy to fall off in the hydrogen absorption and release processes. In addition, pd nanoparticles have a larger specific surface area for hydrogen gas than metallic Pd membranesWhen the sensor is used, hydrogen can be adsorbed on the surface of Pd nano particles from all directions and then is diffused inwards, so that the contact area of gas molecules and Pd is increased, the time of hydrogen adsorption-permeation-diffusion is shortened, and the response speed of the hydrogen sensor can be improved.
On the other hand, the embodiment of the invention also provides a MoS 2 Pd hydrogen-sensitive material, which is prepared by the preparation method, and the macroscopic structure diagram and the atomic structure diagram of the Pd hydrogen-sensitive material are respectively shown in fig. 3 and 4. Embodiment of the invention MoS 2 In the Pd hydrogen sensitive material, metal Pd nano particles and MoS 2 The acting force between the films is stronger, and the problem that Pd is easy to fall off in the hydrogen absorption and release processes can be solved.
In a further aspect of the embodiment of the present invention, the foregoing MoS is further provided 2 Application of Pd hydrogen-sensitive material in fiber grating hydrogen sensor, moS 2 Pd hydrogen-sensitive material is used as hydrogen-sensitive material in fiber grating hydrogen sensor, and has excellent sensitivity and responsiveness.
The embodiment of the invention also provides a preparation method of the fiber bragg grating hydrogen sensor, which comprises the following steps:
1) Etching the fiber cladding on the surface of the fiber Bragg grating by adopting 40wt% hydrofluoric acid to obtain a pretreated fiber;
2) In MoS 2 Spin-coating a drop of PMMA on the surface of the Pd hydrogen-sensitive material, and heating at 100 ℃ for 5-10 min to solidify the PMMA to form a PMMA film; then immersing in 5wt% NaOH solution, and SiO is treated by NaOH 2 Etching of the Si substrate to adhere MoS 2 PMMA film of Pd hydrogen sensitive material and SiO 2 Separating the Si substrate to obtain MoS-loaded substrate 2 -a PMMA film of Pd hydrogen sensitive material;
3) Will be loaded with MoS 2 And (3) attaching a PMMA film of the Pd hydrogen-sensitive material to the pretreated optical fiber, naturally airing, and then processing and packaging to obtain the fiber grating hydrogen sensor.
In the preparation method of the fiber bragg grating hydrogen sensor, moS is adopted 2 Pd as hydrogen sensitive material and PMMA as medium, transferred to the treated fiber by wet etchingThe whole process hardly damages the optical fiber, so that the manufactured fiber grating hydrogen sensor has the advantages of long service life, good stability and capability of rapidly and continuously monitoring hydrogen.
In some specific embodiments, in step 2), the spin-coating is performed at a rotational speed of 2000 to 3000rpm, such as, but not limited to: 2000rpm, 2500rpm, 2800rpm, 3000rpm, etc.; the spin coating time is 45-60 s, such as, but not limited to: 45s, 50s, 55s, 60s, etc.
In some specific embodiments, in step 2), the etching temperature is 50 to 70 ℃, such as, but not limited to: 50 ℃, 75 ℃, 50 ℃, 70 ℃ and the like; etching time is 15-20 min, and non-limiting examples are: 15min, 18min, 20min, etc.
The technical scheme of the present invention will be further described in detail with reference to the following examples, in which conventional apparatuses in the art are used, and experimental methods without specific conditions noted in the examples are conventional methods and conventional conditions well known in the art or according to the methods and conditions suggested by manufacturers. Unless otherwise indicated, the various starting materials used in the examples below are conventional commercial products or may be prepared by known methods.
Example 1
The present embodiment provides a MoS 2 -a method for preparing a Pd hydrogen sensitive material, comprising the steps of:
s1, preparing MoS on a substrate 2 Film and method for producing the same
2.7g MoO 3 Placing the quartz boat on a mica substrate and placing the quartz boat in a tube furnace, and placing a quartz boat containing 1.5g of sulfur powder in the tube furnace so that the distance between the quartz boat and the tube furnace is 20cm; then heating the tube furnace to 850 ℃, and preserving heat for 15min to enable MoO 3 React with sulfur vapor to form MoS 2 And deposited on a mica substrate to obtain a MoS-loaded substrate 2 Mica matrix of the film;
s2, preparing a conductive substrate
In SiO 2 Coating PMMA (polymethyl methacrylate) on half area of the surface of the Si substrate, and heating at 100 ℃ for 10min to cure the PMMA to form a PMMA film; however, the method is thatThen the Cr/Au (10 nm/100 nm) metal film is thermally evaporated on the whole substrate surface, and then the substrate is immersed into acetone with the temperature of 65 ℃, the Cr/Au metal film coated on the PMMA film can fall off along with the dissolution of the PMMA film, so that SiO 2 Only half of the area on the surface of the Si substrate is plated with a Cr/Au metal film, thus obtaining the conductive substrate;
S3，MoS 2 transfer of film
The load obtained in step S1 is MoS 2 Spin-coating a drop of PMMA on the surface of the mica substrate of the film, and heating at 100 ℃ for 10min to solidify the PMMA to form a PMMA film; immersing in deionized water, sticking MoS by water surface tension 2 Separating the PMMA film of the thin film from the mica substrate; then sticking MoS 2 The PMMA film of the film is stuck on the conductive substrate obtained in the step S2, and is dried, and after the moisture between the PMMA film and the conductive substrate is evaporated, moS is stuck due to the intermolecular van der Waals force 2 The PMMA film of the film is tightly attached to the conductive substrate; finally, immersing the mixture in a hot acetone solution at 65 ℃ for 15min to obtain MoS 2 Dissolving and falling PMMA film on the surface of the film, cleaning by adopting deionized water and isopropanol in sequence, and drying by using nitrogen to obtain surface-loaded MoS 2 A conductive substrate of the film;
s4, preparing electroplating solution
Dissolving 0.53g of palladium chloride and 3.1mL of 36% concentrated hydrochloric acid in 1000mL of deionized water, uniformly mixing to obtain palladium chloride hydrochloric acid solution, and using the palladium chloride hydrochloric acid solution as electroplating solution for preparing metal Pd nano-particles by an electrochemical deposition method;
s5, performing electrochemical deposition on MoS 2 Controllable deposition of Pd nanoparticles on thin films
Loading MoS on the surface obtained in the step S3 2 Immersing the conductive substrate of the film into electroplating solution, performing electrochemical deposition at constant potential of-0.20V vs SCE, and immersing into deionized water to remove residual electroplating solution after 5s deposition to obtain MoS 2 -Pd hydrogen sensitive material.
As shown in FIG. 5a, the MoS produced in this example 2 Atomic force microscope image of Pd Hydrogen sensitive Material, as can be seen in the figure, moS of this example 2 On the filmThe diameter of the deposited Pd nanoparticles was about 2nm.
Example 2
MoS of the present embodiment 2 Preparation of Pd Hydrogen-sensitive Material and MoS of example 1 2 The preparation process of the Pd-hydrogen sensitive material is similar, the only difference being that: in this embodiment, the deposition time in step S5 is 10S.
As shown in FIG. 5b, the MoS produced in this example 2 Atomic force microscope image of Pd Hydrogen sensitive Material, as can be seen in the figure, moS of this example 2 The diameter of the Pd nanoparticles deposited on the film was about 9nm.
Example 3
MoS of the present embodiment 2 Preparation of Pd Hydrogen-sensitive Material and MoS of example 1 2 The preparation process of the Pd-hydrogen sensitive material is similar, the only difference being that: in this embodiment, the deposition time in step S5 is 15S.
As shown in FIG. 5c, the MoS produced in this example 2 Atomic force microscope image of Pd Hydrogen sensitive Material, as can be seen in the figure, moS of this example 2 The diameter of the Pd nanoparticles deposited on the film was about 16nm.
Example 4
MoS of the present embodiment 2 Preparation of Pd Hydrogen-sensitive Material and MoS of example 1 2 The preparation process of the Pd-hydrogen sensitive material is similar, the only difference being that: in this embodiment, the deposition time in step S5 is 30S.
As shown in FIG. 5d, the MoS obtained in this example 2 Atomic force microscope image of Pd Hydrogen sensitive Material, as can be seen in the figure, moS of this example 2 The diameter of the Pd nanoparticles deposited on the film was about 36nm.
FIG. 6 shows MoS obtained in examples 1 to 4 of the present invention 2 The graph of the diameter of Pd nano-particles in Pd hydrogen sensitive material and the deposition time shows that the diameter of Pd nano-particles is approximately in linear relation with the deposition time, so that the MoS can be flexibly regulated and controlled by regulating the deposition time 2 The size of Pd nano particles in the Pd hydrogen sensitive material, thereby meeting the actual requirements of the hydrogen sensor under different working conditions.
Comparative example 1
MoS of this comparative example 2 Preparation of Pd Hydrogen-sensitive Material and MoS of example 4 2 The preparation process of the Pd hydrogen-sensitive material is similar, with the difference that: in the preparation method of the comparative example, the step S4 is not included, and in the step S5 of the comparative example, the magnetron sputtering mode is adopted in MoS 2 A Pd metal film of about 36nm was sputtered on the film.
Comparative example 2
MoS of this comparative example 2 Preparation of Pd Hydrogen-sensitive Material and MoS of example 4 2 The preparation process of the Pd hydrogen-sensitive material is similar, with the difference that: in this comparative example, in step S5, electrochemical deposition was performed at a constant potential of-0.10V vs SCE.
As shown in FIG. 7, the MoS obtained in this comparative example 2 Atomic force microscope image of Pd hydrogen sensitive material, it can be seen from the figure that MoS prepared in this comparative example 2 In Pd hydrogen sensitive material, moS 2 The diameter of the Pd nanoparticles deposited on the film was about 10nm.
As is evident from comparative example 4 and comparative example 2, the same electrochemical deposition method was employed for a deposition time of 30s, but the results showed that the electrochemical deposition was performed at a constant potential of-0.20V vs SCE in example 4, which produced MoS 2 The diameter of Pd nano-particles in the Pd hydrogen sensitive material is about 36nm, and the nucleation density is large; while comparative example 2, in which electrochemical deposition was carried out at a constant potential of-0.10V vs SCE, produced MoS 2 The diameter of Pd nano-particles in the Pd hydrogen sensitive material is only about 10nm, and the nucleation density is smaller. Therefore, the invention further illustrates that the nucleation density of Pd nano-particles can be improved by performing electrochemical deposition under the constant potential of-0.20V vs SCE.
Experimental example 1
The MoS prepared in example 4 was used in this experimental example 2 Pd hydrogen sensitive material is used as the hydrogen sensitive material of the fiber grating hydrogen sensor to prepare the fiber grating hydrogen sensor.
The preparation method of the fiber bragg grating hydrogen sensor comprises the following steps:
1) Etching the fiber cladding on the surface of the fiber Bragg grating by adopting 40wt% hydrofluoric acid to obtain a pretreated fiber;
2) At 3000rpm, at MoS 2 Spin-coating a drop of PMMA on the surface of the Pd hydrogen-sensitive material, spin-coating for 60s, and heating at 100 ℃ for 5-10 min to cure the PMMA to form a PMMA film; then immersing in 5wt% NaOH solution, at 50deg.C, siO is treated with NaOH 2 Etching of the Si substrate to adhere MoS 2 PMMA film of Pd hydrogen sensitive material and SiO 2 separating/Si substrate, and etching for 15min to obtain MoS loaded substrate 2 -a PMMA film of Pd hydrogen sensitive material;
3) Will be loaded with MoS 2 A PMMA film of Pd hydrogen sensitive material is stuck on the pretreated optical fiber, and naturally dried, moS 2 The PMMA film on the surface of the Pd hydrogen sensitive material is directly used as a protective layer without being removed; and finally, processing and packaging to obtain the fiber bragg grating hydrogen sensor.
And carrying out a hydrogen detection experiment on the prepared fiber bragg grating hydrogen sensor: the prepared fiber bragg grating hydrogen sensor is placed in a gas chamber, and hydrogen with the concentration of 1% is introduced to detect the real-time cyclic response condition of the fiber bragg grating hydrogen sensor to the hydrogen with the concentration of 1%, and the test result is shown in fig. 8.
As can be seen from fig. 8, when the hydrogen concentration increases from 0 to 1%, the wavelength shifts significantly, the wavelength shifts to 105pm, the sensor sensitivity to 105pm/%, and the sensitivity is higher; the response time and the recovery time of the sensor are 25s and 40s respectively, meanwhile, the wavelength fluctuation is small, and the stability of the sensor is good. Compared with the Pd-based fiber grating hydrogen sensor of the same type, the sensor has excellent performance.
The test results show that the embodiment of the invention is based on MoS 2 The fiber bragg grating hydrogen sensor of the Pd hydrogen-sensitive material can rapidly and continuously monitor hydrogen, and has good sensitivity, responsiveness and stability.
Experimental example 2
The MoS prepared in comparative example 1 was used in this experimental example 2 Pd hydrogen-sensitive material used as hydrogen-sensitive material of fiber grating hydrogen sensor for preparing fiber grating hydrogen sensor, and the fiber grating hydrogen sensorThe preparation method of (2) was the same as that in experimental example 1.
The hydrogen detection experiment is carried out on the fiber bragg grating hydrogen sensor prepared in the experimental example: the prepared fiber bragg grating hydrogen sensor is placed in a gas chamber, and hydrogen with the concentration of 1% is introduced to detect the real-time cyclic response condition of the fiber bragg grating hydrogen sensor to the hydrogen with the concentration of 1%, and the test result is shown in fig. 9.
As can be seen from fig. 9, when the hydrogen concentration was first increased from 0 to 1%, the wavelength was shifted 80pm, the sensor sensitivity was 80pm/%, and the response time and recovery time of the sensor were 80s and 110s, respectively; in the last two experiments, the wavelength drift is 45pm, the sensitivity of the sensor is 45pm/%, the response time and the recovery time of the sensor are respectively 100s and 140s, the wavelength fluctuation is large, and the performance of the sensor is attenuated.
From the above results, it can be seen that the method of electrochemical deposition is carried out on MoS 2 Compared with the deposition of Pd nano particles on a film, the method of magnetron sputtering is used for depositing Pd nano particles on MoS 2 Sputtering Pd metal film on the film, because of Pd metal film and MoS 2 Binding force of (C) is weaker than that of Pd nano-particles and MoS 2 The binding force of the fiber grating hydrogen sensor leads to the phase change of partial Pd metal film easily occurring in the reaction process of the fiber grating hydrogen sensor and the embrittlement and the falling of the Pd metal film, thereby leading to the sensitivity reduction of the fiber grating hydrogen sensor and the performance attenuation under multiple tests; compared with Pd nano particles, the Pd metal film has smaller specific surface area, so that the contact area of hydrogen molecules and Pd is reduced, and the time of hydrogen adsorption-permeation-diffusion is longer, so that the prepared fiber grating hydrogen sensor has longer response time and recovery time; furthermore, compared to electrochemical deposition methods, magnetron sputtering is not a non-destructive process, resulting in a prepared MoS 2 Pd hydrogen sensitive material quality is reduced.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (8)
1. MoS (MoS) 2 -a process for the preparation of a Pd hydrogen sensitive material, characterized in that it comprises the steps of:
s1, growing MoS on a substrate by adopting a chemical vapor deposition method 2 Film, get MoS loaded 2 A substrate of the film;
s2, preparing a conductive substrate;
s3, moS on the substrate 2 Transferring the film onto the conductive substrate to obtain a loaded MoS 2 A conductive substrate of the film;
s4, preparing palladium chloride hydrochloric acid solution as electroplating solution;
s5, loading the MoS on the load 2 Immersing the conductive substrate of the film into the electroplating solution, performing electrochemical deposition under constant potential, and immersing into deionized water to remove residual electroplating solution to obtain the MoS 2 -a Pd hydrogen sensitive material;
in the step S2, the method for preparing the conductive substrate is: in SiO 2 Evaporating a metal film on the surface of the Si substrate to obtain the conductive substrate; the vapor deposition area of the metal film occupies the SiO 2 30% -50% of the surface area of the 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; the thickness of the Cr metal film is 6-10 nm; the thickness of the Au metal film is 60-100nm; in the Ti/Au metal film, the thickness ratio of the Ti metal film to the Au metal film is 1:10; the thickness of the Ti metal film is 6-10 nm; the thickness of the Au metal film is 60-100 nm;
in the step S5, the constant potential is-0.20V vs SCE, and the electrochemical deposition time is 5-30S.
2. MoS according to claim 1 2 A process for preparing Pd hydrogen-sensitive material, characterized in that in step S1, moS is grown on a substrate 2 The method for the film comprises the following steps: in MoO 3 And sulfur powder as reaction raw materials, and growing MoS on a substrate by a chemical vapor deposition method 2 Film, get MoS loaded 2 A substrate of the film; the MoO 3 The molar ratio of the sulfur powder to the sulfur powder is 1:2.5-1:3; the temperature of the chemical vapor deposition is 820-850 ℃ and the time is 10-15 min; the matrix is any one of mica, silicon wafer or sapphire.
3. MoS according to claim 1 2 A process for the preparation of Pd hydrogen-sensitive materials, characterized in that in said step S3, moS is transferred 2 The method for the film comprises the following steps: moS on the substrate is etched by a wet method by taking PMMA as a medium 2 The film is transferred to the conductive substrate.
4. MoS according to claim 1 2 -a preparation method of a Pd hydrogen-sensitive material, wherein in the step S4, the method for preparing a palladium chloride hydrochloric acid solution is as follows: dissolving palladium chloride and concentrated hydrochloric acid in deionized water, and uniformly mixing to obtain a palladium chloride hydrochloric acid solution; the molar concentration ratio of the palladium chloride to the concentrated hydrochloric acid is 0.03:1-0.04:1.
5. MoS (MoS) 2 -a Pd hydrogen sensitive material, characterized in that the MoS 2 -Pd-hydrogen sensitive material prepared by the preparation method according to any one of claims 1-4.
6. The MoS of claim 5 2 Pd hydrogen-sensitiveThe application of the material in the fiber bragg grating hydrogen sensor is characterized in that the MoS 2 Pd hydrogen-sensitive material is used as hydrogen-sensitive material in fiber grating hydrogen sensor.
7. The preparation method of the fiber bragg grating hydrogen sensor is characterized by comprising the following steps of:
1) Etching the fiber cladding on the surface of the fiber Bragg grating by adopting 40wt% hydrofluoric acid to obtain a pretreated fiber;
2) In MoS 2 Spin-coating a drop of PMMA on the surface of the Pd hydrogen-sensitive material, and heating to cure the PMMA to form a PMMA film; then immersing in 5wt% NaOH solution, and SiO is treated by NaOH 2 Etching of the Si substrate to adhere MoS 2 PMMA film of Pd hydrogen sensitive material and SiO 2 Separating the Si substrate to obtain MoS-loaded substrate 2 PMMA film of Pd hydrogen sensitive material, said MoS 2 -Pd-hydrogen sensitive material prepared by the preparation method of any one of claims 1-4;
3) Will be loaded with MoS 2 And (3) attaching a PMMA film of the Pd hydrogen-sensitive material to the pretreated optical fiber, naturally airing, and then processing and packaging to obtain the fiber grating hydrogen sensor.
8. The method for manufacturing a fiber bragg grating hydrogen sensor according to claim 7, wherein in the step 2), the spin-coating speed is 2000-3000 rpm, and the spin-coating time is 45-60 s; the etching temperature is 50-70 ℃, and the etching time is 15-20 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202310542209.XA CN116288234B (en) | 2023-05-15 | 2023-05-15 | MoS (MoS) 2 Pd hydrogen sensitive material and preparation method thereof |
Applications Claiming Priority (1)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105334245A (en) * | 2015-11-10 | 2016-02-17 | 湖北大学 | Making method for molybdenum oxide nano-fiber paper hydrogen sensor |
| KR20210003517A (en) * | 2019-07-02 | 2021-01-12 | 연세대학교 산학협력단 | Gas Sensor with Two-dimensional Transition Metal Dichalcogenide Based on Schottky Barrier Control and Fabrication Method Thereof |
| CN112881476A (en) * | 2021-01-20 | 2021-06-01 | 湖北大学 | Response type adjustable two-dimensional semiconductor room temperature hydrogen sensor and manufacturing method thereof |
| CN115418621A (en) * | 2022-10-24 | 2022-12-02 | 中国华能集团清洁能源技术研究院有限公司 | Controllable preparation method of palladium-based hydrogen-sensitive material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105334245A (en) * | 2015-11-10 | 2016-02-17 | 湖北大学 | Making method for molybdenum oxide nano-fiber paper hydrogen sensor |
| KR20210003517A (en) * | 2019-07-02 | 2021-01-12 | 연세대학교 산학협력단 | Gas Sensor with Two-dimensional Transition Metal Dichalcogenide Based on Schottky Barrier Control and Fabrication Method Thereof |
| CN112881476A (en) * | 2021-01-20 | 2021-06-01 | 湖北大学 | Response type adjustable two-dimensional semiconductor room temperature hydrogen sensor and manufacturing method thereof |
| CN115418621A (en) * | 2022-10-24 | 2022-12-02 | 中国华能集团清洁能源技术研究院有限公司 | Controllable preparation method of palladium-based hydrogen-sensitive material |
Non-Patent Citations (1)
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| Hao et al..Highly Enhanced H2 Sensing Performance of Few-Layer MoS2/SiO2/Si Heterojunctions by Surface Decoration of Pd Nanoparticles.《Nanoscale Research Letters》.2017,第2页方法部分. * |
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