CN114477290B - Sodium tungsten bronze nanosheet array SERS substrate and preparation method and application thereof - Google Patents
Sodium tungsten bronze nanosheet array SERS substrate and preparation method and application thereof Download PDFInfo
- Publication number
- CN114477290B CN114477290B CN202210166702.1A CN202210166702A CN114477290B CN 114477290 B CN114477290 B CN 114477290B CN 202210166702 A CN202210166702 A CN 202210166702A CN 114477290 B CN114477290 B CN 114477290B
- Authority
- CN
- China
- Prior art keywords
- sodium
- array
- tungsten bronze
- nanoplatelet
- sers
- 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.)
- Active
Links
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 49
- 239000000758 substrate Substances 0.000 title claims abstract description 47
- 239000002135 nanosheet Substances 0.000 title claims abstract description 42
- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 33
- 239000010974 bronze Substances 0.000 title claims abstract description 33
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- CZIMGECIMULZMS-UHFFFAOYSA-N [W].[Na] Chemical compound [W].[Na] CZIMGECIMULZMS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 52
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 20
- 239000011521 glass Substances 0.000 claims abstract description 19
- 238000001514 detection method Methods 0.000 claims abstract description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003491 array Methods 0.000 claims abstract description 11
- 238000004729 solvothermal method Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
The invention discloses a sodium tungsten bronze nano-sheet array SERS substrate, a preparation method and application thereof, which is prepared from tungsten powder and H 2 O 2 WO doped with sodium by solvothermal method on glass substrate by using isopropanol as solvent 3 ·0.33H 2 O nanoplatelet arrays, then go through H 2 High temperature reduction to obtain Na y WO 3‑x An array of nanoplatelets. The sodium tungsten bronze nano-sheet array with the surface plasmon property prepared by the invention can be used as an SERS substrate, and the detection limit of the sodium tungsten bronze nano-sheet array on MB is 10 ‑7 M, exhibits good SERS stability and uniformity.
Description
Technical Field
The invention belongs to the technical field of surface-enhanced Raman scattering detection, and particularly relates to a sodium tungsten bronze nanosheet array SERS substrate and a preparation method and application thereof.
Background
The Surface Enhanced Raman Scattering (SERS) effect is initially defined as a raman enhancement effect that originates from noble metal surfaces. Under the background, noble metal nano structures are widely researched and applied in the fields of chemical identification, biological sensing, environmental analysis and the like. In the last two decades, a long development has been made in the preparation of noble metal-based SERS substrates with high sensitivity, good selectivity and good reproducibility. However, noble metal nanostructures suffer from the disadvantages of high manufacturing costs and poor biocompatibility. Therefore, the expansion of SERS onto semiconductor plasmonic materials that also have Surface Plasmon (SPR) properties has attracted considerable attention. Compared with noble metals, the Local Surface Plasmon Resonance (LSPR) of the plasmon semiconductor can be regulated and controlled by the size and the shape, and can be regulated and controlled by the change of the concentration of free carriers caused by doping, temperature or phase change, so that the application range of the plasmon semiconductor material as an SERS substrate is greatly widened. By introducing oxygen vacancies or doping interstitial atoms, the free carrier concentration in the metal oxide semiconductor can be increased. When the free carrier concentration is high enough, it can be made to behave like a metal LSPR, thus having potential applications in SERS.
As an important application field of plasmonic materials, SERS applications based on nonmetallic plasmonic materials have emerged and developed rapidly in recent years. For example, chinese patent CN105621486a discloses a preparation method based on emerging molybdenum oxide semiconductor material with plasma characteristics as SERS active substrate, firstly preparing molybdenum oxide nanoplatelets with different plasmon intensities and frequencies by solvothermal method, then removing surface defect state species (Mo 5+ And oxygen vacancies), forming a core-shell structure of MoO 3-x @MoO 3 The nano-sheet can be applied to SERS detection, and the detection limit can reach 10 -7 M is comparable to noble metal nanostructures, with the bluest position of the LSPR absorption center at 750 nm. In addition, chinese patent CN111495355A prepared a WO 3-x Nanosheet photocatalyst, realizing WO 3-x Absorption and control of LSPR in the visible region and excellent catalytic degradation to methyl orange, however, the WO 3-x The nanosheets can catalyze and degrade target molecules, and cannot be applied to SERS detection.
Although in recent years oxygen deficient metal oxides (in particular WO 3-x And MoO 3-x ) Extensive research has been conducted, but there is limited research on the surface plasmon properties and applications of another important nonmetallic plasmon tungsten bronze material. Molecular formula M x WO 3 (0.ltoreq.x.ltoreq.1, M is usually Li, na, K, rb, cs) tungsten bronze has essentially angle sharing WO 6 Octahedral perovskite structure, while metal M is inserted in perovskite B site. In the tungsten bronze family, sodium tungsten bronze has been of great interest since discovery, and its electrical and optical properties can be varied on a large scale by varying the sodium content. Chinese patent CN113184911a discloses a preparation method of a porous sodium tungsten bronze octahedron, which is to add sodium tungstate and ammonium fluoride into a mixed solution of deionized water and ethanol, and obtain the porous sodium tungsten bronze octahedron through hydrothermal reaction and subsequent annealing treatment in an argon/hydrogen mixed atmosphere, wherein the material has good catalytic performance for electrocatalytic water electrolysis hydrogen production.
So far, no reports have been made about SERS properties and applications of plasmonic sodium tungsten bronze. Meanwhile, in the previous work, the plasmonic metal oxide powder is directly used as a SERS substrate, which is disadvantageous in signal reproducibility and inconvenient in SERS detection operation. Therefore, the sodium doping scheme with simple and environment-friendly technology and easy operation is researched, so that the sodium tungsten bronze with the plasmon property is prepared, and the sodium tungsten bronze is applied to SERS detection, is a subject with scientific and technical value, and has great significance in expanding the application of the plasmon sodium tungsten bronze.
Disclosure of Invention
In order to solve the problem that the traditional sodium tungsten bronze material has no LSPR absorption in the visible light range, and expand the application of the plasmonic sodium tungsten bronze by exploring the SERS performance of the sodium tungsten bronze material, the invention provides a simple preparation method of a sodium tungsten bronze nano-sheet array with plasmonic characteristics, and the oxygen-deficient sodium tungsten bronze nano-sheet array with a visible light absorption band is obtained by in-situ doping sodium on a glass substrate and performing thermal reduction in a hydrogen atmosphere, so that the oxygen-deficient sodium tungsten bronze nano-sheet array can be used as a SERS substrate.
The invention adopts the following technical scheme for realizing the purpose:
a preparation method of a sodium tungsten bronze nanosheet array SERS substrate is characterized by comprising the following steps of: by tungsten powder and H 2 O 2 WO doped with sodium by solvothermal method on glass substrate by using isopropanol as solvent 3 ·0.33H 2 O nanoplatelet arrays, then go through H 2 High temperature reduction to obtain Na y WO 3-x The nanoplatelet array SERS substrate.
The preparation method of the invention specifically comprises the following steps:
step 1, adding tungsten powder into hydrogen peroxide solution, magnetically stirring until the tungsten powder is clear, adding isopropanol and uniformly mixing; then transferring the mixed solution into a polytetrafluoroethylene container of a reaction kettle, putting the clean glass substrate into the polytetrafluoroethylene container downwards, reacting for 8-15 h at 150-180 ℃, cooling to room temperature, taking out, washing and drying to obtain the sodium-doped WO on the glass substrate 3 ·0.33H 2 O nanosheet arrayThe method comprises the steps of carrying out a first treatment on the surface of the Due to the strong acidity and high temperature of the mixed solution during solvothermal reaction, the top surface of the glass substrate is etched, the main component Na of the glass 2 SiO 3 Releasing sodium into solution, WO as growth adulterated with sodium 3 ·0.33H 2 Sodium source of O nanoplatelet arrays.
Step 2, in order to trigger surface plasmons of tungsten oxide, in a tube furnace, in H 2 Ar/H at 10% by volume 2 Heating to 450-490 ℃ under the mixed atmosphere, and adding sodium into WO 3 ·0.33H 2 Performing heat treatment on the O nano-sheet array substrate for 3-5 h to obtain Na y WO 3-x The nanoplatelet array SERS substrate.
Further, in the step 1, the mass concentration of the hydrogen peroxide solution is 30%, and the mass volume ratio of the tungsten powder to the hydrogen peroxide solution to the isopropanol is 0.6-0.8 g: 3-8 mL: 20-50 mL, preferably 0.72g:5mL:30mL.
Further, in step 1, the solvothermal reaction conditions are preferably 160℃for 12 hours.
Further, in step 2, the conditions for high temperature reduction are preferably 470℃heat treatment for 4 hours.
Further, in step 2, the heating rate is preferably 5℃per minute.
The sodium tungsten bronze nano-sheet array with the surface plasmon property prepared by the invention can be used as an SERS substrate. Using the dye molecule Methylene Blue (MB) as a probe molecule, na was revealed y WO 3-x SERS performance of the nanoplatelet arrays. The results indicate that Na y WO 3-x The detection limit of the nanosheet array on MB is 10 -7 M, exhibits good SERS stability and uniformity.
The beneficial effects of the invention are as follows:
1. the invention prepares the plasmonic sodium tungsten bronze nano-sheet array with oxygen vacancy on the glass substrate simply by in-situ sodium intercalation and subsequent hydrogen reduction, and uses dye molecule Methylene Blue (MB) as probe molecule to reveal Na y WO 3-x The surface enhanced Raman scattering performance and the application of the nano-sheet array. The invention realizes Na y WO 3-x The nanosheet array absorbs in the visible localized surface plasmon resonance band centered at 558nm, which is the absorption peak of the shortest wavelength of sodium tungsten bronze. Based on this unique surface plasmon property, na y WO 3-x The nano-sheet array shows good Surface Enhanced Raman Scattering (SERS) effect, and the detection limit of the nano-sheet array on methylene blue is 10 -7 M. In addition, as a SERS substrate, na y WO 3-x The nano-sheet array not only ensures high SERS signal stability and uniformity, but also is easier and more convenient to operate compared with common plasmon semiconductor material powder. Thus, low cost, readily available, uniform, oxygen deficient Na y WO 3-x The nanoplatelet arrays exhibit a broad range of plasmonic application potential.
2. The invention prepares Na y WO 3-x The nano-sheet array SERS substrate has simple process and environment-friendly process.
Drawings
FIG. 1 is a view of Na prepared in example 1 y WO 3-x An optical photograph of the nanoplatelet array;
FIG. 2 is a view of Na prepared in example 1 y WO 3-x SEM images of the nanoplatelet arrays (inset is a top-view SEM);
FIG. 3 is a view of Na prepared in example 1 y WO 3-x XRD pattern of the nanoplatelet array;
FIG. 4 is a view of Na prepared in example 1 y WO 3-x XPS full spectrum of the nanoplatelet array;
FIG. 5 is a view of Na prepared in example 1 y WO 3-x XPS spectrum of O1s of the nano-sheet array;
FIG. 6 is a sodium-doped WO prepared in example 1 3 ·0.33H 2 O nanosheet array (H) 2 Before heat treatment) and Na y WO 3-x Nanosheet array (H) 2 After heat treatment) UV-VIS-NIR light absorption spectrum;
FIG. 7 (a) is 10 -5 MB of M at H 2 Raman spectra on the substrate before and after heat treatment were compared; FIG. 7 (b) is a view of the composition of Na y WO 3-x 10 collected on nanoplatelet array substrate -3 M～10 -7 Raman spectrum of MB of M.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples, which are given for illustrative purposes only and are not intended to limit the invention in any way.
Example 1
This example prepares Na with plasmonic properties as follows y WO 3-x Nanoplatelet arrays:
step 1, adding 0.72g tungsten powder into 5mL of 30% hydrogen peroxide solution, magnetically stirring for 30min to clarify, and adding 30mL of isopropanol ((CH) 3 ) 2 CHOH) and mixing well; then transferring the mixed solution into a polytetrafluoroethylene container of a reaction kettle, putting the clean glass substrate into the polytetrafluoroethylene container downwards, reacting for 12 hours at 160 ℃, then cooling to room temperature, taking out, washing with ethanol and deionized water in sequence, and drying at 60 ℃ overnight to obtain the sodium-doped WO on the glass substrate 3 ·0.33H 2 An array of O nanoplatelets.
Step 2, in order to trigger surface plasmons of tungsten oxide, in a tube furnace, in H 2 Ar/H at 10% by volume 2 Heating to 470 ℃ at a heating rate of 5 ℃/min under a mixed atmosphere, and adding sodium into the WO 3 ·0.33H 2 Performing heat treatment on the O nano-sheet array substrate for 4 hours to obtain Na with plasmon property y WO 3-x The nanoplatelet array is stored in a vacuum dryer for further use.
The prepared samples were characterized analytically using Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible-near infrared spectrophotometry (UV-VIS-NIR) techniques. SERS spectra were collected on a confocal raman system (Renishaw, insia) fitted with a 50-fold objective.
FIG. 1 shows Na prepared in this example y WO 3-x An optical photograph of the nanoplatelet array, the sample exhibits a black appearance.
FIG. 2 shows Na prepared in this example y WO 3-x Nanosheet arraySEM images of the columns (inset is a top-view SEM). It can be seen that hexagonal Na y WO 3-x The nanoplatelet arrays are grown on the glass substrate in a very close staggered manner, and the grown thickness is about 1.4 μm and covers the whole surface of the glass substrate.
FIG. 3 shows Na prepared in this example y WO 3-x XRD pattern of the nanoplatelet array. According to the PDF card, the sample is hexagonal Na 0.3 WO 3 (PDF # 00-046-0174), which shows that sodium released by etching of glass is doped into the lattice of the sample due to the strong acidity and high temperature of the precursor solution during solvothermal reaction, followed by H with high temperature 2 And (3) thermally reducing, wherein sodium is inserted into the B site of the perovskite to form sodium tungsten bronze.
FIG. 4 shows Na prepared in this example y WO 3-x The XPS full spectrum of the nanoplatelet array can see a distinct Na1s peak position, indicating that sodium was successfully doped into tungsten oxide. As shown in FIG. 5, for Na y WO 3-x Analysis of XPS spectrum of O1s of the nano-sheet array shows 531.6eV binding energy peak related to oxygen vacancy, which proves the existence of oxygen vacancy.
FIG. 6 shows the synthesized sodium-doped WO of this example 3 ·0.33H 2 O nanosheet array (H) 2 Before heat treatment) and Na y WO 3-x Nanosheet array (H) 2 After heat treatment). It can be seen that, through H 2 The heat-treated sample showed LSPR absorption in the visible region, and showed a strong LSPR absorption band centered at 558nm, almost equivalent to that of gold nanoparticles. The absorption peaks cover the entire visible range, resulting in a black appearance as shown in fig. 1. Visible LSPR absorption is considered to be due to H 2 The high concentration of free charge carriers generated in the heat treatment is responsible for this as evidenced by the oxygen vacancies revealed by the XPS spectrum of fig. 5.
To test the SERS performance of the substrate, samples (1.2 cm×0.2 cm) were immersed in 500 μlmb ethanol solutions of different concentrations for 30min. The substrate was then placed on a glass slide and ethanol was naturally evaporated for raman spectroscopy. SERS spectra were acquired using a laser with a wavelength of 633nm as the excitation light source. The effective laser power for single acquisition was 0.085mW and the exposure time was 50s.
As shown in FIG. 7 (a), and use 10 -5 WO with MMB as probe doped with sodium 3 ·0.33H 2 O nanosheet array (H) 2 Before heat treatment), na y WO 3-x Nanosheet array (H) 2 After heat treatment) exhibits a significantly stronger raman signal response, indicating Na y WO 3-x The SERS effect of the nanoplatelet array is improved. To further reveal Na y WO 3-x SERS enhancement of nanoplatelet arrays, 10 detected -3 M to 10 -7 MB solutions of different concentrations within the M range. As shown in FIG. 7 (b), a successful detection of as low as 10 -7 M MB solution, and can be identified as MB at 1629cm -1 Characteristic peaks at the same time.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. A preparation method of a sodium tungsten bronze nanosheet array SERS substrate is characterized by comprising the following steps of: by tungsten powder and H 2 O 2 WO doped with sodium by solvothermal method on glass substrate by using isopropanol as solvent 3 ·0.33H 2 O nanoplatelet arrays, then go through H 2 High temperature reduction to obtain Na y WO 3-x Nanosheet array SERS substrate, the Na y WO 3-x The nano-sheet array SERS substrate is used in SERS detection; during the solvothermal reaction, the top surface of the glass substrate is etched, the main component Na of the glass 2 SiO 3 Releasing sodium into solution, WO as growth adulterated with sodium 3 ·0.33H 2 Sodium source of O nanoplatelet arrays.
2. The method for preparing a sodium tungsten bronze nano-sheet array SERS substrate according to claim 1, comprising the steps of:
step 1, adding tungsten powder into peroxyMagnetically stirring the mixture in the hydrogen sulfide solution until the mixture is clear, adding isopropanol and uniformly mixing the isopropanol and the isopropanol; then transferring the mixed solution into a polytetrafluoroethylene container of a reaction kettle, putting the clean glass substrate into the polytetrafluoroethylene container downwards, reacting for 8-15 h at 150-180 ℃, cooling to room temperature, taking out, washing and drying to obtain the sodium-doped WO on the glass substrate 3 ·0.33H 2 An O nanoplatelet array;
step 2, in order to trigger surface plasmons of tungsten oxide, in a tube furnace, in H 2 Ar/H at 10% by volume 2 Heating to 450-490 ℃ under the mixed atmosphere, and adding sodium into WO 3 ·0.33H 2 Performing heat treatment on the O nano-sheet array substrate for 3-5 h to obtain Na y WO 3-x The nanoplatelet array SERS substrate.
3. The method for preparing the sodium tungsten bronze nano-sheet array SERS substrate according to claim 2, which is characterized in that: in the step 1, the mass concentration of the hydrogen peroxide solution is 30%, and the mass volume ratio of the tungsten powder to the hydrogen peroxide solution to the isopropanol is 0.6-0.8 g: 3-8 mL: 20-50 mL.
4. The method for preparing the sodium tungsten bronze nano-sheet array SERS substrate according to claim 2, which is characterized in that: in the step 2, the temperature rising rate is 5 ℃/min.
5. A sodium tungsten bronze nanoplatelet array SERS substrate prepared by the method of any one of claims 1 to 4.
6. Use of a sodium tungsten bronze nano-sheet array SERS substrate according to claim 5 in SERS detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210166702.1A CN114477290B (en) | 2022-02-23 | 2022-02-23 | Sodium tungsten bronze nanosheet array SERS substrate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210166702.1A CN114477290B (en) | 2022-02-23 | 2022-02-23 | Sodium tungsten bronze nanosheet array SERS substrate and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114477290A CN114477290A (en) | 2022-05-13 |
| CN114477290B true CN114477290B (en) | 2024-03-01 |
Family
ID=81482966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210166702.1A Active CN114477290B (en) | 2022-02-23 | 2022-02-23 | Sodium tungsten bronze nanosheet array SERS substrate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114477290B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63242946A (en) * | 1987-03-31 | 1988-10-07 | Kawatetsu Kogyo Kk | Glass ceramics and their production |
| JP2001354424A (en) * | 2000-06-08 | 2001-12-25 | Japan New Metals Co Ltd | Method for manufacturing heteropolytungstic acid |
| CN111495355A (en) * | 2020-04-26 | 2020-08-07 | 中国科学院合肥物质科学研究院 | WO with visible light region L SPR absorption3-xPhotocatalyst, preparation method and application |
| CN114392734A (en) * | 2021-12-29 | 2022-04-26 | 北京工业大学 | Tungsten oxide composite material and preparation method and application thereof |
-
2022
- 2022-02-23 CN CN202210166702.1A patent/CN114477290B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63242946A (en) * | 1987-03-31 | 1988-10-07 | Kawatetsu Kogyo Kk | Glass ceramics and their production |
| JP2001354424A (en) * | 2000-06-08 | 2001-12-25 | Japan New Metals Co Ltd | Method for manufacturing heteropolytungstic acid |
| CN111495355A (en) * | 2020-04-26 | 2020-08-07 | 中国科学院合肥物质科学研究院 | WO with visible light region L SPR absorption3-xPhotocatalyst, preparation method and application |
| CN114392734A (en) * | 2021-12-29 | 2022-04-26 | 北京工业大学 | Tungsten oxide composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王其和,黄庆兵.电致变色WO_3薄膜的结构与光电性能研究.南京大学学报(自然科学版).1997,(04),摘要、第1部分. * |
| 电致变色WO_3薄膜的结构与光电性能研究;王其和, 黄庆兵;南京大学学报(自然科学版)(04);摘要、第1部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114477290A (en) | 2022-05-13 |
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 | |
| Lu et al. | Fabrication of core-shell Au-Pt nanoparticle film and its potential application as catalysis and SERS substrate | |
| Wang et al. | Composition-adjustable Ag–Au substitutional alloy microcages enabling tunable plasmon resonance for ultrasensitive SERS | |
| Song et al. | Defect engineering in semiconductor-based SERS | |
| Zhao et al. | Monitoring catalytic degradation of dye molecules on silver-coated ZnO nanowire arrays by surface-enhanced Raman spectroscopy | |
| Vadivel et al. | Effect of Mg doping on structural, optical and photocatalytic activity of SnO 2 nanostructure thin films | |
| Ibrahim | Photocatalytic activity of nanostructured ZnO–ZrO2 binary oxide using fluorometric method | |
| Khajehpour et al. | Gold nanothorns–macroporous silicon hybrid structure: A simple and ultrasensitive platform for SERS | |
| Gürbüz et al. | A study of the influences of transition metal (Mn, Ni) co-doping on the morphological, structural and optical properties of nanostructured CdO films | |
| Su et al. | Electrochemically assisted photocatalytic degradation of phenol using silicon-doped TiO2 nanofilm electrode | |
| Teodorescu-Soare et al. | Growth and characterization of TiO2 nanotube arrays under dynamic anodization. Photocatalytic activity | |
| Du et al. | Quasi-metal microwave route to MoN and Mo2C ultrafine nanocrystalline hollow spheres as surface-enhanced Raman scattering substrates | |
| Liu et al. | Single-crystalline indium hydroxide and indium oxide microcubes: synthesis and characterization | |
| Borah et al. | Tailoring the crystalline phase and size of the MoO3 quantum dots via sonication induced modified top-down method | |
| Horti et al. | Synthesis and optical properties of copper oxide nanoparticles: effect of solvents | |
| Tang et al. | Na y WO3–x Nanosheet Array via In Situ Na Intercalation for Surface-Enhanced Raman Scattering Detection of Methylene Blue | |
| Yadav et al. | Synthesis and characterization of graphene oxide-based nanofluids and study of their thermal conductivity | |
| CN114477290B (en) | Sodium tungsten bronze nanosheet array SERS substrate and preparation method and application thereof | |
| Zhao et al. | SERS-active Ag nanoparticles embedded in glass prepared by a two-step electric field-assisted diffusion | |
| CN105290414A (en) | Method for synthesizing nano-copper particles | |
| Ratchagar et al. | Synthesis and characterization of SnO2 nano particles for carbon absorbing applications | |
| Song et al. | Effect of surface physics of metal oxides on the ability to form metallic nanowires | |
| Mai et al. | Structural, Optical and Photocatalytic Properties of Cu2+ Doped ZnO Nanorods with Using HMTA Solvent Prepared by Hydrothermal Method | |
| Keerthana et al. | Hydrothermally synthesized Ag decorated β-Ga2O3 heterostructures as low cost, reusable SERS substrates for the nanomolar detection of rhodamine 6G | |
| Krasil’nikov et al. | Synthesis and photocatalytic properties of low-dimensional cobalt-doped zinc oxide with different crystal shapes |
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 |