CN113109315A - MoS2Au/Ag heterostructure, preparation method and application - Google Patents
MoS2Au/Ag heterostructure, preparation method and application Download PDFInfo
- Publication number
- CN113109315A CN113109315A CN202110318736.3A CN202110318736A CN113109315A CN 113109315 A CN113109315 A CN 113109315A CN 202110318736 A CN202110318736 A CN 202110318736A CN 113109315 A CN113109315 A CN 113109315A
- Authority
- CN
- China
- Prior art keywords
- mos
- heterostructure
- preparation
- substrate
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 138
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 131
- 239000002105 nanoparticle Substances 0.000 claims abstract description 50
- 239000002135 nanosheet Substances 0.000 claims abstract description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052709 silver Inorganic materials 0.000 claims abstract description 33
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 28
- 239000004332 silver Substances 0.000 claims abstract description 28
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 71
- 239000000084 colloidal system Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000011065 in-situ storage Methods 0.000 claims description 15
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 7
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims description 2
- 210000004080 milk Anatomy 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 239000010931 gold Substances 0.000 abstract description 109
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 11
- 238000012986 modification Methods 0.000 abstract description 7
- 238000010183 spectrum analysis Methods 0.000 abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 46
- 101000674278 Homo sapiens Serine-tRNA ligase, cytoplasmic Proteins 0.000 description 27
- 101000674040 Homo sapiens Serine-tRNA ligase, mitochondrial Proteins 0.000 description 27
- 102100040516 Serine-tRNA ligase, cytoplasmic Human genes 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000001237 Raman spectrum Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910015667 MoO4 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 Transition Metal Sulfides Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- 229910017745 AgNP Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 210000002706 plastid Anatomy 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004557 single molecule detection Methods 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Thermal Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to the technical field of spectral analysis, in particular to a MoS2/Au/Ag heterostructure, preparation method and application thereof, and MoS2The nano-sheet grows vertically on the conductive glass, MoS2Au and Ag are attached to the surface of the silver nanoparticle in sequence, and the diameter of the Au nanoparticle is smaller than that of the Ag nanoparticle. Gold and silver bimetal with different grain diameters is prepared and combined with a halfConductor MoS2Forming a ternary heterostructure (named MoS) on FTO conductive glass as a support layer modification2Au/Ag), the smaller AuNPs and the larger AgNPs are cooperatively matched, so that not only can the SERS performance be effectively further improved, but also the PEC activity can be simultaneously improved, and the uniformity and the reproducibility are better.
Description
Technical Field
The invention relates to the technical field of spectral analysis, in particular to a MoS2Au/Ag heterostructure, preparation method and application.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
MoS2Is a typical two-dimensional (2D) layered Transition Metal Sulfides (TMDs), and has been widely studied in recent years in various application fields due to its excellent electronic and optoelectronic properties, especially in SERS sensors and photo-electrochemical (PEC) water degradation. SERS is a powerful spectral analysis technique, and can provide high-resolution vibration information and realize label-free single-molecule detection. Based on MoS2The SERS substrate of (a) is largely due to charge transfer between the substrate and the molecule and coupling between dipoles. PEC water splitting is considered to be the most efficient clean, economical, and environmentally friendly way to produce hydrogen (H)2) The method of (1).
Simple MoS2This limits its ability to achieve low concentration detection since only chemical enhancement mechanisms can produce weaker SERS activity. Moreover, although much success has been achieved in PEC based on molybdenum disulfide materials, its low conductivity and high charge recombination rate remain key issues limiting its catalytic applications. Thus, MoS2Heterostructures incorporating noble metal Nanoparticles (NPs) are investigated to improve MoS2SERS and PEC performance of (a). For example, Zuo et al have studied an in situ modification of nanoparticles to MoS2Method on nanosheets to obtain metal-MoS2Nanometer isoThe structure of the plastid has obvious hydrogen evolution reactivity and SERS sensitivity. ZHEN et al demonstrate MoS2The coupling effect of the/Au heterojunction can enhance the water splitting and SERS performance of the PEC. Dong et al reported a method of using the enzyme in MoS2The ultra-fast electron transfer heterostructure composed of Pt nanoparticles grown in situ at the edge position of the nanosheet has high PEC performance and SERS activity.
However, the inventors have found that the above materials have limited ability to synergistically enhance PEC and SERS performance and suffer from poor uniformity and reproducibility, and thus, it remains a serious challenge to provide a substrate having both excellent SERS performance and PEC activity.
Disclosure of Invention
In order to solve the above problems existing in the prior art, the present disclosure provides a MoS2The preparation method and application of the/Au/Ag heterostructure comprises the steps of preparing gold and silver double metals with different grain diameters and combining a semiconductor MoS2Forming a ternary heterostructure (named MoS) on FTO conductive glass as a support layer modification2Au/Ag), the smaller AuNPs and the larger AgNPs are cooperatively matched, so that not only can the SERS performance be effectively further improved, but also the PEC activity can be simultaneously improved, and the uniformity and the reproducibility are better.
Specifically, the technical scheme of the present disclosure is as follows:
in a first aspect of the present disclosure, a MoS is provided2/Au/Ag heterostructure, MoS2The nano-sheet grows vertically on the conductive glass, MoS2Au and Ag are attached to the surface of the silver nanoparticle in sequence, and the diameter of the Au nanoparticle is smaller than that of the Ag nanoparticle.
In a second aspect of the present disclosure, a MoS is provided2The preparation method of the Au/Ag heterostructure comprises the following steps: preparation of vertically grown MoS on conductive glass by hydrothermal method2Nanosheets; then, modifying Au nanoparticles on MoS by an in-situ reduction method2Nano-sheets; finally, the Au-modified MoS2The nanosheet substrate further supports Ag nanoparticles by electrostatic adsorption.
In a third aspect of the present disclosure, a MoS2Au/Ag heterostructure and/or MoS obtained by the preparation method2the/Au/Ag heterostructure is applied to new energy sources and sensors.
One or more technical schemes in the disclosure have the following beneficial effects:
(1) vertical growth MoS prepared by hydrothermal method2The nanoplatelets can provide a larger surface area and more active sites, resulting in a higher density of "hot spots" and faster charge transfer rates.
(2) The bimetallic-semiconductor composite structure can introduce multiple surface plasmon couplings through size effects, which plays a crucial role in synergistically enhancing both SERS and PEC performance. Through the reaction with MoS2、MoS2Au and MoS2Comparison with the Ag substrate proves the proposed MoS2The SERS enhancement and PEC water splitting performance of the/Au/Ag heterostructure is the most excellent.
(3) MoS vertically grown on FTO substrate2The nano-sheets are beneficial to controlling the sizes of Au and Ag nano-particles, and the small-size Au and large-size Ag modified MoS can be quickly and efficiently obtained by controlling the concentration and reaction time of a metal solution in the in-situ reduction reaction process and controlling a silver colloid solution used for electrostatic adsorption2A nanosheet heterostructure. The preparation method is convenient, and the structure is simple to control and efficient.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to limit the disclosure.
Embodiments of the present disclosure are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is the MoS of example 12Au/Ag, MoS of comparative examples 1 to 32Nanosheet, MoS2Au and MoS2Electron micrograph of/Ag: (a) MoS on FTO substrate2Nanosheet, (b) MoS2/Au,(c)MoS2/Ag,(d)MoS2SEM picture of/Au/Ag; (e) MoS2HRTEM image of/Au/Ag; (f) MoS2SAED/Au/Ag;(g)MoS2,(h)MoS2/Au,(i)MoS2/Ag,(j)MoS2localized electric field distribution of/Au/Ag.
FIG. 2 shows (a) a Raman spectrum and (b) an ultraviolet-visible absorption spectrum of different substrates of example 1 and comparative examples 1 to 3.
FIG. 3 shows the SERS performance test results of different substrate materials of example 1 and comparative examples 1-3: (a) based on MoS2R6G raman spectrum of the substrate; (b) (c) and (e) are each MoS2/Au,MoS2Ag and MoS2R6G Raman spectrum of/Au/Ag substrate; (d) (f) MoS2Ag and MoS2Detecting the linear relation between the intensity and the concentration of R6G on the Au/Ag substrate; (g) (h) uniformity testing of the substrate; (i) reproducibility test of 10 batches of samples.
FIG. 4 shows the PEC performance test results for different substrate materials of example 1 and comparative examples 1-3: (a) MoS2,MoS2/Au,MoS2Ag and MoS2HER polarization curve of Au/Ag substrate under dark and light conditions; (b) a corresponding impedance spectrum (EIS); (c) corresponding overpotential (10 mA/cm) in dark and light2) And initial potential (1 mA/cm)2)；(d)MoS2,MoS2/Au,MoS2Ag and MoS2Photocurrent response of/Au/Ag; (e) and testing the stability of the photocurrent.
Detailed Description
The disclosure is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, and/or combinations thereof, unless the context clearly indicates otherwise.
At present, the structural inhibiting materials in the prior art have limited capability of synergistically improving PEC and SERS performance, and have poor uniformity and reproducibility, and in order to solve the above problems, the present disclosure provides a MoS2Au/Ag heterostructure, preparation method and application.
In one embodiment of the present disclosure, a MoS2/Au/Ag heterostructure, MoS2The nano-sheet grows vertically on the conductive glass, MoS2Au and Ag are attached to the surface of the silver nanoparticle in sequence, and the diameter of the Au nanoparticle is smaller than that of the Ag nanoparticle.
Among them, the vertically grown MoS prepared by hydrothermal method2The nanoplatelets can provide a larger surface area and more active sites, resulting in a higher density of "hot spots" and faster charge transfer rates. Au, Ag and MoS2The composite structure formed by the nanosheets introduces multiple surface plasmon coupling through a size effect, and AuNPs with smaller size and AgNPs with larger size are matched with each other to synergistically enhance the activities of PEC and SER. In addition, the heterostructure has excellent uniformity and reproducibility, Au and Ag nanoparticles cannot fall off in the reaction process of the PEC and the SER, and the structure is stable.
Further, the diameter of the Au nano-particles is 5-10nm, and the diameter of the Ag nano-particles is 40-60 nm. By controlling the Au and Ag nanoparticles within a certain size range, particularly keeping the size difference of the Au and Ag nanoparticles within a reasonable range, the size effect can be played optimally, and the large and small size synergistic enhancement SERS and PEC activities are promoted.
In one embodiment of the present disclosure, a MoS2The preparation method of the Au/Ag heterostructure comprises the following steps: preparation of vertically grown MoS on conductive glass by hydrothermal method2Nanosheets; then, modifying Au nanoparticles on MoS by an in-situ reduction method2Nano-sheets; finally, the Au-modified MoS2The nanosheet substrate further supports Ag nanoparticles by electrostatic adsorption.
Through hydrothermal reaction, vertically grown MoS can be prepared on an FTO substrate2The nano-sheet structure not only can provide abundant adsorption sites for loading of the bimetallic nano-particles, but also can generate higher 'hot spot' density and faster charge transfer speed. MoS decorated with vertical growth2The FTO substrate of the nano-sheet is reduced in situ in the Au-containing solution, the preparation method is simple, and the Au nano-particles and the MoS are prepared2The combination of the nano sheets is tighter, and the structural stability is improved. Meanwhile, the size of the Au nanoparticles can be controlled by adjusting the metal concentration and the reaction time by the in-situ reduction method. In addition, Au-modified MoS2The Ag nano-particles can be obtained by electrostatic adsorption of the nano-sheet substrate, and the preparation method is simple.
Further, the hydrothermal process comprises: dissolving thiourea and sodium molybdate dihydrate in an ethanol water solution, placing the solution in a reaction kettle, and then adding FTO glass for vulcanization reaction.
Further, the molar ratio of thiourea to sodium molybdate dihydrate is 3-5:0.5-1.5, preferably 4: 1; further, the temperature of the vulcanization reaction is 160-200 ℃, preferably 180 ℃; further, the time of the sulfurization reaction is 5 to 8 hours, preferably 7 hours. By controlling the dosage ratio of thiourea to sodium molybdate, the prepared MoS can be ensured2The nano-sheet vertically grows on the FTO substrate, and simultaneously, the temperature and the time of the vulcanization reaction are controlled, thereby being beneficial to realizing MoS2Close arrangement of nanosheets on the substrate and control of MoS2The size of the nanosheets further exposes more of the active adsorption sites.
Further, in-situ reduction is carried out to prepare Au nanoparticle modified MoS2The process of nanosheet includes: mixing MoS2Modified FTO radicalSoaking in HAuCl4In the solution, taking out the substrate after reacting for a period of time, and cleaning and drying the substrate; further, HAuCl4Is 0.5-0.8mM, preferably 0.6 mM; further, the reaction time is 8 to 15min, preferably 10 min. In the process, HAuCl is controlled4The concentration of (a) and the time of the in situ reaction help to obtain small-sized Au nanoparticles. The reaction time is too long, the size of the Au nanoparticles is increased and the Au nanoparticles are accumulated, so that the Au nanoparticles are unevenly distributed. Within the above range, the Au nanoparticles have a small diameter and uniform size, contributing to both Ag adsorption and exposure of more active sites.
Further, the process of electrostatically adsorbing the Ag nanoparticles includes: firstly preparing a silver colloid solution, and then adding MoS2Soaking the Au substrate in a silver colloid solution to electrostatically adsorb the Ag nano particles; further, the silver colloid solution is 15-30 wt% silver colloid solution, preferably 20 wt% silver colloid solution. When the silver colloid solution is in the optimal concentration, the uniform adsorption of Ag nano particles on the Au surface is facilitated, and the condition of metal agglomeration is avoided.
Further, the preparation method of the silver colloid solution comprises the following steps: heating the ethylene glycol oil bath to 60-80 ℃, adding PVP, heating to 120-140 ℃, and adding AgNO3Continuously reacting the powder, stopping heating and stirring when the solution becomes milk green, adding a large amount of acetone after the colloid is cooled, and performing centrifugal separation to obtain a silver colloid solution; the electrostatic adsorption time is 10-14h, preferably 12 h. In the silver colloid solution, the size of Ag nano particles is 40-60nm, and the uniform distribution of the Ag nano particles can be effectively ensured by controlling the electrostatic adsorption time.
In one embodiment of the present disclosure, a MoS for synergistic enhancement of SERS and PEC2Au/Ag heterostructure and/or MoS obtained by the preparation method2the/Au/Ag heterostructure is applied to new energy sources and sensors.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.
Example 1
MoS2The preparation method of the Au/Ag heterostructure comprises the following steps:
first, FTO conductive glass (1X 1 cm) was washed with acetone, alcohol and deionized water (DI water) in this order2) For 20 minutes. Preparation of vertically grown MoS on FTO glass surface by hydrothermal method2Nanosheet: thiourea (CH)4N2S2) and sodium molybdate dihydrate (Na)2MoO4·2H2O3.4 g) was dissolved in 30ml of DI water and 30ml of ethanol solution and stirred until dissolved. The mixed solution was then poured into a 100 ml reaction kettle and placed in a clear FTO glass. Then, the mixture was placed in a laboratory oven and heated at 180 ℃ for 7 hours to complete the vulcanization reaction. And after the heating is finished and the temperature is cooled to the room temperature, taking out the sample, continuously washing the sample by using deionized water, removing excessive molybdenum disulfide and residual solution, and drying the sample in a vacuum oven.
Then, through HAuCl4In-situ reduction to modify AuNPs in MoS2On the nano-chip, MoS is formed2Au heterostructure: preparing the FTO/MoS thus obtained2The substrate was soaked in 0.6mM HAuCl4In solution, AuNPs are generated after 10 minutes of reaction, and then put into clean deionized water for three times to remove residual HAuCl4And (3) solution. Subsequent MoS on FTO glass2The Au substrate is dried in vacuum.
The preparation method of AgNPs comprises the following steps: the method for preparing the 20 wt% silver colloid solution by a chemical reduction mode comprises the following steps: 20ml of ethylene glycol were first heated to 70 ℃ in a magnetic stirred oil bath, at which time 0.25g of PVP was added. The mixture was then heated to 135 c and 0.05g AgNO3 powder was added to react for about 1 hour, and heating and stirring were stopped when the solution turned to a milk-green colloid. Then adding a large amount of acetone after the colloid is cooled, and separating the nano silver particles from the solution. Finally, the precipitate was centrifuged at 12000rpm for 5 minutes in a centrifuge to obtain silver particles, which were dispersed in deionized water, and this procedure was repeated three times to completely wash off the residue, to finally obtain a clean silver colloidal solution. In order to firmly adhere the prepared Ag NPs to the MoS2The surface of Au substrate, placing the substrate in AgNPsThe solution was allowed to stand for 12 hours. Finally, the sample was rinsed with deionized water to remove excess AgNPs and form MoS on the FTO glass2a/Au/Ag structure.
Example 2
MoS2The preparation method of the Au/Ag heterostructure comprises the following steps:
first, FTO conductive glass (1X 1 cm) was washed with acetone, alcohol and deionized water (DI water) in this order2) For 20 minutes. Preparation of vertically grown MoS on FTO glass surface by hydrothermal method2Nanosheet: thiourea (CH)4N2S4.56 g) and sodium molybdate dihydrate (Na)2MoO4·2H2O3.4 g) was dissolved in 30ml of DI water and 30ml of ethanol solution and stirred until dissolved. The mixed solution was then poured into a 100 ml reaction kettle and placed in a clear FTO glass. Then, the mixture was placed in a laboratory oven and heated at 200 ℃ for 8 hours to complete the vulcanization reaction. And after the heating is finished and the temperature is cooled to the room temperature, taking out the sample, continuously washing the sample by using deionized water, removing excessive molybdenum disulfide and residual solution, and drying the sample in a vacuum oven.
Then, through HAuCl4In-situ reduction to modify AuNPs in MoS2On the nano-chip, MoS is formed2Au heterostructure: preparing the FTO/MoS thus obtained2The substrate was soaked in 0.7mM HAuCl4In solution, the AuNPs are formed after 14 minutes of reaction, and then put into clean deionized water for three times to remove residual HAuCl4And (3) solution. Subsequent MoS on FTO glass2The Au substrate is dried in vacuum.
The preparation method of AgNPs comprises the following steps: 20ml of ethylene glycol were first heated to 80 ℃ in a magnetically stirred oil bath, at which time 0.25g of PVP was added. The mixture was then heated to 140 ℃ and 0.05g of AgNO was added3The powder was allowed to react for about 1 hour and heating and stirring were stopped when the solution turned to a milk-green colloid. Then adding a large amount of acetone after the colloid is cooled, and separating the nano silver particles from the solution. Finally, the precipitate was centrifuged at 12000rpm for 5 minutes in a centrifuge to obtain silver particles, which were dispersed in deionized water, and this procedure was repeated three times to completely wash off the residue, to finally obtain a clean silver colloidal solution. To prepareGood Ag NPs firmly adhere to MoS2Au substrate surface, the substrate was placed in AgNPs solution for 12 hours. Finally, the sample was rinsed with deionized water to remove excess AgNPs and form MoS on the FTO glass2a/Au/Ag structure.
Example 3
MoS2The preparation method of the Au/Ag heterostructure comprises the following steps:
first, FTO conductive glass (1X 1 cm) was washed with acetone, alcohol and deionized water (DI water) in this order2) For 20 minutes. Preparation of vertically grown MoS on FTO glass surface by hydrothermal method2Nanosheet: thiourea (CH)4N2S4.56 g) and sodium molybdate dihydrate (Na)2MoO4·2H2O1.52 g) was dissolved in 30ml of DI water and 30ml of ethanol solution and stirred until dissolved. The mixed solution was then poured into a 100 ml reaction vessel and placed in a clear FTO glass. Then, the mixture was placed in a laboratory oven and heated at 150 ℃ for 5 hours to complete the vulcanization reaction. And after the heating is finished and the temperature is cooled to the room temperature, taking out the sample, continuously washing the sample by using deionized water, removing excessive molybdenum disulfide and residual solution, and drying the sample in a vacuum oven.
Then, through HAuCl4In-situ reduction to modify AuNPs in MoS2On the nano-chip, MoS is formed2Au heterostructure: preparing the FTO/MoS thus obtained2The substrate was soaked in 0.5mM HAuCl4In solution, the AuNPs are formed after 14 minutes of reaction, and then put into clean deionized water for three times to remove residual HAuCl4And (3) solution. Subsequent MoS on FTO glass2The Au substrate is dried in vacuum.
The preparation method of AgNPs comprises the following steps: 20ml of ethylene glycol were first heated to 80 ℃ in a magnetically stirred oil bath, at which time 0.25g of PVP was added. The mixture was then heated to 120 ℃ and 0.05g of AgNO was added3The powder was allowed to react for about 1 hour and heating and stirring were stopped when the solution turned to a milk-green colloid. Then adding a large amount of acetone after the colloid is cooled, and separating the nano silver particles from the solution. Finally, the precipitate was centrifuged at 12000rpm for 5 minutes in a centrifuge to obtain a silver particle precipitate, which was dispersed in deionized water for thorough washingResidue, this process was repeated three times to finally obtain a clean silver colloid solution. In order to firmly adhere the prepared Ag NPs to the MoS2Au substrate surface, the substrate was placed in AgNPs solution for 12 hours. Finally, the sample was rinsed with deionized water to remove excess AgNPs and form MoS on the FTO glass2a/Au/Ag structure.
Comparative example 1:
the difference compared to example 1 is that this comparative example 1 only produces MoS2Nanosheets.
Comparative example 2:
the difference compared to example 1 is that comparative example 2 produced MoS2/Au。
Comparative example 3:
the difference compared to example 1 is that comparative example 3 produced MoS2/Ag。
As shown in FIG. 1, the morphology of the prepared substrate was characterized by SEM, and the original FTO glass had a rugged surface as shown in FIG. 1(a), and MoS was grown2Then, the surface is covered with a layer of vertical three-dimensional nanoplatelets by a hydrothermal method (fig. 1 a). Original MoS2The nano-sheets present a closely-arranged lamellar structure, the average wall thickness is 12nm, and the length is 200 nm. FIG. 1(b) is a schematic representation of the reaction by reaction with HAuCl4In-situ reduction to form dense AuNPs attached to MoS2SEM morphology on nanosheets (MoS)2Au substrate) where AuNPs average 8nm in diameter and 3nm inter-particle distance. In MoS2AgNPs (MoS) of surfaces2Ag substrate) as shown in fig. 1(c), the average diameter of AgNPs was about 50 nm. FIG. 1(d) shows a bimetallic composite MoS made of Au-Ag2Hetero structure (MoS)2Au/Ag), wherein the large AgNPs and the small AuNPs are uniformly attached to the MoS2In the above, the vertical nanosheet structure is clearly visible. To further determine and validate the heterostructure, its high resolution transmission electron microscopy images (HRTEM) were characterized as shown in fig. 1(e), where the lattices of small AuNPs, large AgNPs and molybdenum disulfide could be clearly observed, corresponding to 0.235nm, 0.236nm and 0.605nm of Au (111), Ag (111) and MoS, respectively2(003) And the molybdenum disulfide nanosheets can provide an effective substrate for nucleation of AuNPs and support of AgNPs. MoS2Selective Area Electron Diffraction (SAED) of/Au/Ag FIG. 1f shows that the diffraction rings of Au (111) and Ag (111) are clearly visible, corresponding to the crystallographic planes detected by HRTEM. As shown in FIG. 1(g), the original MoS2The electric field intensity of the nanosheet is weak. Under the modification of AuNPs (fig. 1h), due to the LSPR effect of AuNPs, "hot spots" are mainly distributed in the gaps between AuNPs. For MoS2Ag substrates, the electric field is enhanced to a greater extent and is concentrated mainly in the interstices between the particles. For MoS2Au/Ag substrate (figure 1j), a large number of 'hot spots' distributed among AuNPs, AgNPs and AuNPs, forming multiple surface plasmon resonance couplings, wherein the number and intensity of the 'hot spots' are in accordance with MoS2、MoS2/Au、MoS2The Ag substrate contrast is greatly improved.
Different based on MoS2Raman spectra of the substrates are compared in FIG. 2(a), with two representative MoS's in all substrates2A vibration peak. Original MoS after AuNPs, AgNPs and Au-Ag bimetal modification2At 402cm-1The peak at (B) gradually red-shifted to 405cm-1,407cm-1,408cm-1Indicates that the metal nanoparticles and MoS2Stronger interaction exists between the nano sheets. In addition, MoS due to the LSPR action of AuNPs2Both peaks of the Au substrate are enhanced in intensity, whereas MoS2Ag has higher Raman intensity due to the larger local electromagnetic field generated by AgNPs, and for MoS2the/Au/Ag substrate produced the strongest enhancement due to multiple surface plasmon resonance coupling. To understand based on MoS2The optical properties of the samples, their corresponding uv-vis absorption spectra are shown in fig. 2 (a). Due to MoS2The multilayer nanostructures and inherently narrow band gaps exhibit a broad absorption band in the wavelength range above 300nm at the substrate on FTO. After introduction of AgNPs, MoS2The absorption intensity of/Ag in the ultraviolet and visible light range is enhanced, and due to the Local Surface Plasmon Resonance (LSPR) mode of AgNPs, the appearance is clear at 480nmA pronounced absorption peak. Also, MoS2the/Au also shows obvious absorption peak near 550 nm. And MoS2、MoS2Ag and MoS2In comparison with Au, MoS2the/Au/Ag showed the strongest light absorption intensity, with two prominent peaks at 480nm and at 550nm, corresponding to the resonance absorption of AgNPs and AuNPs, confirming the formation of multiple metal nanoparticles.
Performance test experiments:
SERS and PEC performance tests were performed on the products of example 1, comparative documents 1-3:
the SERS performance test procedure is as follows: and 4 microliter of molecular solution is dripped on the surface of the substrate each time for natural drying, and then SERS detection is carried out. A laser having a wavelength of 532nm was used. The laser power is 0.48mW, the integration time is 4s, and the grating selection is 600 g/nm. The laser beam is focused on the substrate using a 50 x objective lens.
And (4) analyzing results:
as in fig. 3, by detection 10-5M R6G molecular Raman Spectroscopy to evaluate the 4 MoS-based molecules2The SERS performance of the sample of (1). As shown in fig. 3(a), the SERS intensity gradually increases with the modification of AuNPs, AgNPs, and Au — Ag bimetals. With the original MoS2、MoS2Au and MoS2MoS/Ag substrate comparison2The SERS performance of Au/Ag substrates is best, mainly due to the multiple surface plasmon coupling effect between AuNPs, AgNPs and Au-Ag bimetals. Furthermore, MoS2The SERS enhancement effect of Ag is superior to that of MoS2Au, since AgNPs can induce a stronger local electric field than AuNPs, whereas the original MoS2The substrate had the worst SERS effect due to the presence of only weak chemical enhancement. To better demonstrate MoS2The enhancement effect of the composite metal substrate is that the Raman spectra of R6G at different concentrations are respectively detected. FIG. 3(b) shows MoS2Raman spectrum of Au, the intensity of Raman peak decreases monotonically with decreasing concentration of R6G, and the limit of detection (LOD) is about 10-8And M. For MoS2Ag, LOD can reach 10-10M (FIG. 3c), although the intensity at this concentration was weak, only 613cm was observed-1And 1360cm-1Characteristic peak of (2). FIG. 3(d) shows the signal at 613cm-1,774cm-1And 1650cm-1The intensity of the SERS peak is linearly related to the logarithm of the concentration of R6G, and the correlation coefficients (R2) are 0.998, 0.980, and 0.944, respectively. MoS can be observed in FIG. 3(e)2Raman spectrum of R6G corresponding to Au/Ag substrate when R6G solution is from 10-5M is diluted to 10-12M, the Raman signal decreases correspondingly at 10-12M, 613cm can still be recognized-1Characteristic peak of (2). And MoS2LOD ratio MoS of Au/Ag substrate 22 orders of magnitude lower/Ag than MoS2the/Au is lower by 4 orders of magnitude. Further, as shown in FIG. 3(f), MoS2the/Au/Ag substrate has good linear relation and is positioned at 613cm-1、774cm-1And 1650cm-1R corresponding to characteristic peak20.997, 0.991 and 0.992, respectively. Thus, these results indicate MoS2the/Au/Ag substrate has the best sensitivity. The minimum detection concentration of the substrate is 10-12M, corresponding to 613cm-1Has a strength of 110 in SiO2Upper detection 10-3The intensity of M was 98. Thus MoS2EF of/Au/Ag substrate is 1.1X 109. Such excellent sensitivity is mainly due to dense hot spots generated by multiple surface plasmon couplings.
It is noted that uniformity and reproducibility play an important role in SERS detection. Thus, in MoS2Randomly selecting 10 points on/Au/Ag substrate to measure 10-6M R6 raman spectrum of 6G (fig. 3 g). The results show that the intensities of the characteristic peaks of each raman spectrum are substantially the same. More intuitively, 613cm in these spectra-1The intensity of the peaks was compared by histogram, as shown in FIG. 3(h), and the RSD value was only 10.47%, indicating good uniformity of the substrate. In addition, FIG. 3(i) shows MoS from 10 lots 210 for detection on Au/Ag substrates-5M R6 613cm of 6G-1、774cm-1And 1650cm-1The intensities of the three main characteristic peaks only slightly fluctuate, and the corresponding RSD values are 10.32%, 15.67% and 15.01%, respectively. Overall, MoS is due to its excellent uniformity and reproducibility2The Au/Ag substrate has wide application prospect in SERS application.
The PEC performance testing procedure was as follows: all photoelectrochemical measurements were performed in a three electrode system using the electrochemical workstation CHI760E at room temperature. Ag/AgCl (saturated potassium chloride) electrode as reference electrode, graphite rod as counter electrode, and 0.5M saturated with argon
The sulfuric acid solution is used as electrolyte. The scan rate of the test polarization curve was 5mV/s and the potential was switched to a reversible hydrogen electrode by increasing 0.197V. The impedance test was carried out at an open circuit potential frequency in the range of 0.1-105Hz and an amplitude of 5 mV. A 300W xenon lamp was used as the light source.
And (4) analyzing results:
FIG. 4(a) is a polarization curve of Hydrogen Evolution Reaction (HER) under dark and light conditions for a series of substrates, wherein the original MoS2The nanosheet has the worst catalytic effect, and the catalytic performance is gradually enhanced along with the increase of AgNP, AuNPs and Au-Ag bimetallic load. Moreover, the same sample has better catalytic effect under visible light irradiation than in the dark. For comparison, FIG. 4(c) shows the corresponding overpotentials (10 mA/cm) for four samples under light and dark conditions2) And initial potential (1 mA/cm)2) The value of (c). Clearly, MoS on FTO glass2the/Au/Ag has the highest catalytic performance under the illumination condition, the overpotential is 124mV, the initial potential is 32mV, which is not only lower than MoS2/Au、MoS2Ag and MoS2But also below its own potential in dark conditions. This is mainly due to the multiple surface plasmon coupling of the ternary structure that allows more efficient electron-hole separation under illumination.
Fig. 4(b) shows Electrochemical Impedance Spectroscopy (EIS) to determine the electron transfer rate in the HER process. It can be clearly observed that MoS2The semi-circle of Au/Ag is far less than MoS2/Au、MoS2Ag and MoS2It shows that the charge transfer resistance is small and the inherent conductivity is high. A smaller half circle under light conditions indicates more efficient charge transfer and stronger PEC performance, which is consistent with the results of the polarization curve. In addition, the photocurrent responses of these four substrates were also examined to further explore their PEC characteristics. As shown in FIG. 4(d), it is apparent that MoS2Au/Ag heterogeneitiesThe structure had the highest photocurrent density of 43.9 muA/cm2Respectively of intensity MoS2,MoS2Ag and MoS29.1, 2.2, 1.4 times of/Au, means excellent light utilization efficiency and charge transmission efficiency, and benefits from the synergistic effect of Au-Ag double metal and molybdenum disulfide nanosheets. To detect MoS2Stability of Au/Ag catalyst substrate electrochemical tests were carried out for a long time. As shown in FIG. 4(e), the photocurrent was always stabilized at 10mA/cm at a potential of 150mV2Furthermore, the SEM image (see inset) after 8 hours of testing is almost unchanged from that before testing, indicating excellent stability of the catalyst.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. MoS2/Au/Ag heterostructure, characterized by MoS2The nano-sheet grows vertically on the conductive glass, MoS2Au and Ag are attached to the surface of the silver nanoparticle in sequence, and the diameter of the Au nanoparticle is smaller than that of the Ag nanoparticle.
2. A MoS according to claim 12The Au/Ag heterostructure is characterized in that the diameter of the Au nano-particles is 5-10nm, and the diameter of the Ag nano-particles is 40-60 nm.
3. MoS2The preparation method of the Au/Ag heterostructure is characterized by comprising the following steps: preparation of vertically grown MoS on conductive glass by hydrothermal method2Nanosheets; then, modifying Au nanoparticles on MoS by an in-situ reduction method2Nano-sheets; finally, the Au-modified MoS2The nano-sheet substrate is absorbed into one by static electricityLoading Ag nano particles.
4. A MoS according to claim 32Method for the production of/Au/Ag heterostructures, characterized in that the hydrothermal method comprises: dissolving thiourea and sodium molybdate dihydrate in an ethanol water solution, placing the solution in a reaction kettle, and then adding FTO glass for vulcanization reaction.
5. A MoS according to claim 42The preparation method of the Au/Ag heterostructure is characterized in that the molar ratio of thiourea to sodium molybdate dihydrate is 3-5:0.5-1.5, preferably 4: 1; further, the temperature of the vulcanization reaction is 160-200 ℃, preferably 180 ℃; further, the time of the sulfurization reaction is 5 to 8 hours, preferably 7 hours.
6. A MoS according to claim 32The preparation method of the Au/Ag heterostructure is characterized in that Au nanoparticle modified MoS is prepared by in-situ reduction2The process of nanosheet includes: mixing MoS2Soaking modified FTO substrate in HAuCl4In the solution, taking out the substrate after reacting for a period of time, and cleaning and drying the substrate; further, HAuCl4Is 0.5-0.8mM, preferably 0.6 mM; further, the reaction time is 8 to 15min, preferably 10 min.
7. A MoS according to claim 32The preparation method of the Au/Ag heterostructure is characterized in that the process of carrying Ag nano particles through electrostatic adsorption comprises the following steps: firstly preparing a silver colloid solution, and then adding MoS2Soaking the Au substrate in a silver colloid solution to electrostatically adsorb the Ag nano particles; further, the silver colloid solution is 15-30 wt% silver colloid solution, preferably 20 wt% silver colloid solution.
8. A MoS according to claim 72The preparation method of the Au/Ag heterostructure is characterized in that the preparation method of the silver colloid solution comprises the following steps: heating the ethylene glycol oil bath to 60-80 ℃, adding PVP,heating to 120 ℃ and 140 ℃, adding AgNO3And (3) continuously reacting the powder, stopping heating and stirring when the solution becomes milk green, adding a large amount of acetone after the colloid is cooled, and performing centrifugal separation to obtain the silver colloid solution.
9. A MoS according to claim 72The preparation method of the Au/Ag heterostructure is characterized in that the electrostatic adsorption time is 10-14h, preferably 12 h.
10. A MoS according to claim 1 or 22/Au/Ag heterostructure and/or MoS obtainable by a method according to any of claims 3 to 92the/Au/Ag heterostructure is applied to new energy sources and sensors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110318736.3A CN113109315B (en) | 2021-03-25 | 2021-03-25 | MoS 2 Au/Ag heterostructure, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110318736.3A CN113109315B (en) | 2021-03-25 | 2021-03-25 | MoS 2 Au/Ag heterostructure, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113109315A true CN113109315A (en) | 2021-07-13 |
| CN113109315B CN113109315B (en) | 2023-04-07 |
Family
ID=76710553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110318736.3A Active CN113109315B (en) | 2021-03-25 | 2021-03-25 | MoS 2 Au/Ag heterostructure, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113109315B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849798A (en) * | 2012-08-29 | 2013-01-02 | 北京化工大学 | Molybdenum disulfide nano-sheet film material and its preparation methods |
| CN106381481A (en) * | 2016-09-18 | 2017-02-08 | 河南师范大学 | Preparation method of metal doping molybdenum disulfide thin film |
| CN106525812A (en) * | 2016-10-31 | 2017-03-22 | 山东师范大学 | Molybdenum disulfide/gold nanoparticle mixed structure biosensor material and preparation method thereof |
| CN107598182A (en) * | 2017-07-24 | 2018-01-19 | 西北工业大学 | Gold nano grain molybdenum disulfide gold hypersensitive SERS base materials and preparation method |
| CN108226137A (en) * | 2018-01-31 | 2018-06-29 | 山东师范大学 | A kind of flexible, transparent molybdenum disulfide@Argent grains/three-dimensional pyramid structure PMMA SERS substrates preparation method and application |
| CN109467126A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院上海硅酸盐研究所 | A kind of metallic element doping molybdenum disulfide film material and preparation method thereof |
-
2021
- 2021-03-25 CN CN202110318736.3A patent/CN113109315B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849798A (en) * | 2012-08-29 | 2013-01-02 | 北京化工大学 | Molybdenum disulfide nano-sheet film material and its preparation methods |
| CN106381481A (en) * | 2016-09-18 | 2017-02-08 | 河南师范大学 | Preparation method of metal doping molybdenum disulfide thin film |
| CN106525812A (en) * | 2016-10-31 | 2017-03-22 | 山东师范大学 | Molybdenum disulfide/gold nanoparticle mixed structure biosensor material and preparation method thereof |
| CN107598182A (en) * | 2017-07-24 | 2018-01-19 | 西北工业大学 | Gold nano grain molybdenum disulfide gold hypersensitive SERS base materials and preparation method |
| CN109467126A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院上海硅酸盐研究所 | A kind of metallic element doping molybdenum disulfide film material and preparation method thereof |
| CN108226137A (en) * | 2018-01-31 | 2018-06-29 | 山东师范大学 | A kind of flexible, transparent molybdenum disulfide@Argent grains/three-dimensional pyramid structure PMMA SERS substrates preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| JIHUA XU ET AL: "3D SERS substrate based on Au-Ag bi-metal nanoparticles/MoS2 hybrid with pyramid structure", 《OPTICS EXPRESS》, vol. 26, no. 17, 20 August 2018 (2018-08-20), pages 21546 - 21577 * |
| MOHAMMAD AL-MAMUN ET AL: "Directly hydrothermal growth of ultrathin MoS2 nanostructured films as high performance counter electrodes for dye-sensitised solar cells", 《RSC ADVANCES》, vol. 4, 30 April 2014 (2014-04-30), pages 21277 * |
| YINAN ZHENG ET AL: "Nano Ag-Decorated MoS2 Nanosheets from 1T to 2H Phase Conversion for Photocatalytically Reducing CO2 to Methanol", 《ENERGY TECHNOLOGY》, vol. 7, no. 11, 6 August 2019 (2019-08-06), pages 1900582 * |
| 卢伟伟: "《无机纳米材料在环境保护和检测中的应用》", 30 September 2019, 原子能出版社, pages: 144 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113109315B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tan et al. | Plasmonic MoO 3− x@ MoO 3 nanosheets for highly sensitive SERS detection through nanoshell-isolated electromagnetic enhancement | |
| Zhang et al. | A facile ultrasonic-assisted fabrication of nitrogen-doped carbon dots/BiOBr up-conversion nanocomposites for visible light photocatalytic enhancements | |
| Wu et al. | Photocatalytic activity of Ag/TiO 2 nanotube arrays enhanced by surface plasmon resonance and application in hydrogen evolution by water splitting | |
| Hsu et al. | Synthesis of novel Cu2O micro/nanostructural photocathode for solar water splitting | |
| Han et al. | Effect of oxidation on surface-enhanced Raman scattering activity of silver nanoparticles: a quantitative correlation | |
| Chen et al. | Development of RGO@ MoS2@ Ag ternary nanocomposites with tunable geometry structure for recyclable SERS detection | |
| Yang et al. | One-pot synthesis of monodispersed silver nanodecahedra with optimal SERS activities using seedless photo-assisted citrate reduction method | |
| Hsiao et al. | ZnO/Cu 2 O/Si nanowire arrays as ternary heterostructure-based photocatalysts with enhanced photodegradation performances | |
| Kong et al. | N doped carbon dot modified WO3 nanoflakes for efficient photoelectrochemical water oxidation | |
| Xia et al. | CdS quantum dots modified CuO inverse opal electrodes for ultrasensitive electrochemical and photoelectrochemical biosensor | |
| Sheng et al. | Remarkable SERS detection by hybrid Cu2O/Ag nanospheres | |
| CN105866098B (en) | A kind of Cu2Compound micro particles surface-enhanced Raman scattering activity substrate of O-Au and preparation method thereof | |
| Su et al. | The surface-plasmon-resonance and band bending effects on the photoluminescence enhancement of Ag-decorated ZnO nanorods | |
| Xu et al. | Ag nanoparticles anchored organic/inorganic Z-scheme 3DOMM-TiO2–x-based heterojunction for efficient photocatalytic and photoelectrochemical water splitting | |
| Bhardwaj et al. | Fabrication of efficient dye-sensitized solar cells with photoanode containing TiO 2–Au and TiO 2–Ag plasmonic nanocomposites | |
| Yang et al. | Hierarchically rough CuO/Ag composite film with controlled morphology as recyclable SERS-active substrate | |
| Daniel et al. | Absorption spectra and photocurrent densities of Ag nanoparticle/TiO 2 composite thin films with various amounts of Ag | |
| Pham et al. | Enhance Raman scattering for probe methylene blue molecules adsorbed on ZnO microstructures due to charge transfer processes | |
| Bian et al. | Uniformly Dispersed and Controllable Ligand‐Free Silver‐Nanoparticle‐Decorated TiO2 Nanotube Arrays with Enhanced Photoelectrochemical Behaviors | |
| Shiao et al. | Novel gold dendritic nanoflowers deposited on titanium nitride for photoelectrochemical cells | |
| Srivastava et al. | Effect of Ti 1− x Fe x O 2 photoanodes on the performance of dye-sensitized solar cells utilizing natural betalain pigments extracted from Beta vulgaris (BV) | |
| Shinde et al. | Plasmonic Au nanoparticles sensitized ZnO/CuO heterostructure for efficient photoelectrochemical water splitting | |
| Bhardwaj et al. | Significant enhancement of power conversion efficiency of dye-sensitized solar cells by the incorporation of TiO2–Au nanocomposite in TiO2 photoanode | |
| CN113109315B (en) | MoS 2 Au/Ag heterostructure, preparation method and application | |
| Xia et al. | Long-distance transfer of plasmonic hot electrons across the Au–Pt porous interface for the hydrogen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |