CN116818745B - Rapid detection method of rhodamine 6G - Google Patents
Rapid detection method of rhodamine 6G Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 23
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 44
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
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- 206010012434 Dermatitis allergic Diseases 0.000 description 1
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- 239000002156 adsorbate Substances 0.000 description 1
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- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 231100000219 mutagenic Toxicity 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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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
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- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to the field of environmental analysis, in particular to a rapid detection method of rhodamine 6G. The method comprises the following steps: dripping a sample to be tested into WO 3‑x -signal acquisition is performed on the Au flexible SERS substrate by a Raman spectrometer; wherein, the laser wavelength 785 nm, the scanning time 15 s and the integration times are 1. The SERS substrate material provided by the invention has the advantages of good SERS enhancement effect, strong rhodamine 6G response selectivity, high cost performance and simple pretreatment, and can realize rapid detection of rhodamine 6G in aqueous solution.
Description
Technical Field
The invention relates to the field of environmental analysis, in particular to a rapid detection method of rhodamine 6G.
Background
Rhodamine 6G is a typical phenolic printing and dyeing dye derivative, is easily converted with quinone compounds in an acidic printing and dyeing wastewater water body, is a main organic pollutant of the printing and dyeing wastewater, and is one of the most difficult to treat and the most harmful organic pollutants. Previous studies have shown that rhodamine 6G causes allergic dermatitis, stimulates the eyes, skin and respiratory system, and is even involved in mutagenic and teratogenic effects of cells, tissues and organisms. Rhodamine 6G is used as a typical cationic dye, has good water solubility and strong polarity, is extremely easy to remain in environmental water, and can be enriched through a food chain, so that the occurrence concentration and toxicity are gradually amplified, and huge negative effects are caused on the water ecological system and human health. Therefore, the method for researching and monitoring the occurrence form and content of rhodamine 6G in the environmental medium has important significance for environmental supervision and human health.
In order to accurately evaluate the water quality state and pollution level of the environmental water body, it is important to establish an effective and accurate dye analysis method. Common dye analysis methods in laboratories include spectrophotometry, high Performance Liquid Chromatography (HPLC), liquid chromatography-mass spectrometry (HPLC-MS) and the like. The spectrophotometry has low analysis cost, but is easy to be interfered by environmental media, and the accuracy is difficult to reach the analysis requirement; the high performance liquid chromatography has high detection precision, but the sample needs to be subjected to complex pretreatment for matrix purification and target enrichment; the liquid chromatography-mass spectrometry has good separation effect and high sensitivity, but has high instrument cost and high professional requirements for operators. Therefore, the research of an economic, rapid and efficient rhodamine 6G on-site rapid analysis technology is a key point in the field of environmental analysis.
The surface enhanced Raman spectrum technology is focused in the environmental field due to the advantages of no damage and rapidness, and provides a direction for establishing a rhodamine 6G on-site rapid analysis method. Raman scattering effect is found by a indian physicist Raman in 1928, surface enhanced Raman scattering (Surface Enhanced Raman Scattering, abbreviated as SERS) phenomenon of pyridine is observed on a rough silver electrode for the first time in 1974, the SERS effect realizes single molecule detection by 1997, and SERS is widely applied to directions of adsorbate interface orientation and configuration, conformational research, structural analysis and the like. The high-efficiency application of the SERS technology mainly depends on SERS substrates, only a few noble metals and a few transition metals have SERS performance at present, and the substrates are often complex in preparation process and high in cost, are not beneficial to large-scale application and bring great difficulty to the actual detection process.
Disclosure of Invention
The invention aims to provide a rapid detection method of rhodamine 6G. The invention adopts WO 3-x Sea urchin-shaped nano particles are used as a substrate, and active sites such as oxygen vacancies and the like on the surface of the substrate are used for anchoring Au nano particles to prepare WO 3-x The Au composite nano-particles not only improve the stability of Au loading, but also avoid the aggregation phenomenon of the Au particles caused by environmental media. Meanwhile, the physical enhancement mechanism and WO of the Au nano-particles can be fully exerted 3-x Chemical enhancement mechanism of sea urchin-like nanoparticles to enhance WO 3-x SERS enhancement effect of Au complex nanoparticles. WO is incorporated into 3-x Transfer of Au composite nanoparticles to filter paper by drop coating to prepare WO 3-x The Au flexible SERS substrate can effectively avoid the pretreatment step of a sample, and the rhodamine 6G is realized in WO by adopting a dripping or soaking method 3-x And the enrichment of the surface of the Au flexible substrate reduces the pretreatment time and improves the detection efficiency.
In order to achieve the above object, the present invention provides the following solutions:
one of the technical proposal of the invention, a WO 3-x The preparation method of the sea urchin-shaped nano particles comprises the following steps:
WCl (WCl) 6 Dissolving in organic solvent, heating, centrifuging to obtain solid, sequentially cleaning, and drying to obtain WO 3-x Sea urchin-like nanoparticles; wherein x=0-1;
the heating temperature is 160-200 deg.f o C, time is 8-18 h.
The heating temperature is too low to generate a needed crystal structure, and the heating temperature is too high to self-assemble into a sea urchin structure; the heating time is too short to generate a strip-shaped or rod-shaped monomer structure, and the heating time is too long to cause the generated sea urchin structure to be easily deformed loosely.
Further, the WCl 6 The mass volume ratio of the organic solvent to the organic solvent is 0.3-0.5 g:30-50 mL; the organic solvent is absolute ethyl alcohol; the drying temperature was 60 o C, time of 12h。
In a second technical scheme of the invention, the WO prepared by the preparation method 3-x Sea urchin-like nanoparticles.
In a third aspect of the present invention, a method for producing a liquid crystal display device is provided 3-x -Au complex nanoparticle preparation method comprising the steps of:
WO as described above 3-x Adding sea urchin-like nanoparticle into HAuCl 4 Dispersing in the solution uniformly, and irradiating with mercury lamp to obtain the product containing the WO 3-x -a solution of Au complex nanoparticles.
Further, the HAuCl 4 The mass concentration of the solution is 0.002% -0.2%; HAuCl 4 Too low a concentration does not form Au nanoparticles, too high a concentration results in agglomeration of the Au nanoparticles formed, and therefore, the present invention preferably defines HAuCl 4 The mass concentration of the solution is 0.002% -0.2%; said WO 3-x Sea urchin-like nanoparticles and HAuCl 4 The mass volume ratio of the solution is 10-20 mg:10-20 mL, WO 3-x Too high a proportion of Au to be uniformly distributed on the surface thereof, HAuCl 4 Too high a ratio of Au nanoparticles in WO 3-x Agglomeration of the surface occurs, so that the invention preferably defines WO 3-x Sea urchin-like nanoparticles and HAuCl 4 The mass volume ratio of the solution is 10-20 mg:10-20 mL; the irradiation intensity of the mercury lamp is 120 mw/cm 2 The time is 15-30 min, au nano particles cannot be effectively reduced and generated due to too short illumination time, and the size of the Au nano particles can be gradually changed to greatly reduce the SERS effect due to too long illumination time, so that the time for limiting the illumination of the mercury lamp is 15-30 min.
The invention provides a fourth technical scheme, namely the WO prepared by the preparation method 3-x -Au complex nanoparticles.
The invention provides a fifth technical scheme, namely the WO 3-x -use of Au-composite nanoparticles in SERS substrates.
The invention provides a sixth technical scheme, a WO 3-x -Au flexible SERS substrate preparation method comprising the steps of:
WO as described above 3-x -AuTransferring the composite nano particles to filter paper by a dripping method, and air-drying to obtain the WO (WO) 3-x -Au flexible SERS substrate; in particular, the above WO 3-x Centrifuging and concentrating the solution of the Au composite nano-particles, transferring the solution onto filter paper by a dripping method, and air-drying to obtain the WO (WO) 3-x -Au flexible SERS substrate.
The seventh technical scheme of the invention is that the WO prepared by the preparation method 3-x -Au flexible SERS substrate.
The invention provides a method for rapidly detecting rhodamine 6G, which comprises the following steps: enriching the sample to be tested into the WO by dripping or soaking method 3-x -signal acquisition is performed on the Au flexible SERS substrate by a Raman spectrometer; wherein, the laser wavelength 785 nm, the scanning time 15 s and the integration times are 1.
The technical conception of the invention is as follows:
the invention synthesizes WO at first 3-x Sea urchin-like nanoparticles, sea urchin-like WO 3-x The specific surface area is larger, and at the same time WO 3-x The surface is negatively charged, so that positive cationic dye rhodamine 6G molecules can be better adsorbed and enriched; in WO 3-x Design and preparation of WO for substrates 3-x Au composite nano particles, which not only utilize physical enhancement mechanism of Au, but also exert WO 3-x The chemical enhancement mechanism of (2) effectively improves the SERS enhancement effect; WO to be synthesized 3-x The Au composite nano particles are prepared into a 2D film structure, so that agglomeration and inactivation of the nano particles are prevented during sample measurement, the sample pretreatment time is shortened, and the detection efficiency is improved.
The invention discloses the following technical effects:
the invention synthesizes WO by hydrothermal method 3-x (x has a value in the range of 0 to 1, i.e. WO 3-x Is between WO 2 And WO 3 Intermediate valence state oxide) sea urchin-like nano-particles, and synthesizing WO by reduction method 3-x -Au composite nanoparticles, finally preparing WO by drip coating 3-x -Au flexible surface enhanced raman substrate (SERS substrate material). The rhodamine 6G is realized in WO by adopting a dripping or soaking method 3-x Enrichment of the surface of the Au flexible substrate and by portabilityThe raman spectrometer observes the raman characteristic peak of rhodamine 6G. A series of experiments prove that the SERS substrate material preparation method and the target pollutant analysis method adopted by the invention are simple and convenient to operate, and can realize the rapid detection of rhodamine 6G in aqueous solution.
The invention provides a SERS substrate material which has the advantages of good SERS enhancement effect, strong selectivity to rhodamine 6G response, high cost performance and simple pretreatment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram of WO prepared in example 1 of the present invention 3-x Sea urchin-like nanoparticles and WO 3-x -transmission electron micrographs of Au composite nanoparticles; wherein (a) is WO 3-x A low-power TEM image of sea urchin-like nanoparticles, (b) WO 3-x High-power TEM image of sea urchin-like nanoparticle, (c) is WO 3-x XRD spectrum of sea urchin-like nanoparticle, wherein (d) is WO 3-x -low-power TEM image of Au complex nanoparticle, (e) WO 3-x High-power TEM image of Au composite nanoparticles, (f) is WO 3-x XRD spectrum of Au composite nanoparticle.
FIG. 2 shows the WO of the invention prepared in example 1 at various concentrations of rhodamine 6G 3-x Raman spectrum of surface of Au flexible SERS substrate (a), rhodamine 6G concentration and 1365 cm -1 A linear relationship (b) established by the raman peak intensities.
FIG. 3 is a diagram of WO prepared in example 1 of the present invention 3-x -homogeneity evaluation of rhodamine 6G detection by Au flexible SERS substrate; wherein (a) is the same WO 3-x Randomly selecting a Raman spectrum of 16 sample points on the surface of the Au flexible SERS substrate, wherein (b) rhodamine 6G is 1365 cm for the 16 sample points -1 At the raman peak intensity value.
FIG. 4 shows WO prepared in example 1 of the present invention 3-x -evaluation of anti-interference performance of Au flexible SERS substrate on rhodamine 6G detection.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the examples and comparative examples of the present invention, unless otherwise specified, were all available commercially.
The filter paper used in the embodiment of the invention is a glass fiber filter membrane, and the pore diameter is 0.2 mu m.
Example 1
Step 1, WO 3-x Preparation of sea urchin-like nanoparticles:
weigh WCl 6 Adding the reagent 0.4 g into the liner of a 100 mL reaction kettle, adding 40 mL absolute ethyl alcohol, and magnetically stirring until WCl is obtained 6 The powder dissolved until the solution became clear and clear. Transferring the inner container of the reaction kettle into the outer shell of the reaction kettle, putting into a drying oven, and setting the temperature to be 180 DEG C o And C, setting the heating time to be 12 h. After heating, naturally cooling the reaction kettle, centrifuging at 12000 rpm for 10 min, separating solid from liquid, collecting solid particles, repeatedly cleaning the solid collected after centrifuging with absolute ethyl alcohol for 5 times, and then placing in a vacuum drying oven for 60 times o Drying under C12-h, oven drying, grinding into powder with mortar to obtain WO 3-x Sea urchin-shaped nanoparticle with specific surface area of 34 cm 2 /g。
Step 2, WO 3-x -preparation of Au complex nanoparticle solution:
preparing a series of HAuCl with concentration gradient of 0.2%, 0.1%, 0.02%, 0.01%, 0.002% 4 ·4H 2 O solution, taking the formulated HAuCl 4 ·4H 2 O solution 15 and mL, and respectively weighing WO prepared in step 1 3-x Sea urchin-like nanoparticle 10 mg is added to the above series of HAuCl 4 ·4H 2 The mixed solution is obtained from the O solution by using a magnetic stirrer 25 o C stirring at 400 rpm at normal temperature for 5min until the powder is dispersed. With continuous stirring, the irradiation intensity was 120 mw/cm 2 The mercury lamp irradiates the above WO 3-x And HAuCl 4 ·4H 2 Mixing the solution of O for 20 min; obtaining WO 3-x Au composite nanoparticle solution (corresponding to HAuCl) 4 ·4H 2 Concentration of O solution prepared WO 3-x The Au composite nano-particles are respectively marked as WO 3-x -Au-0.2, WO 3-x -Au-0.1, WO 3-x -Au-0.02, WO 3-x -Au-0.01, WO 3-x -Au-0.002）。
Step 3, WO 3-x -preparation of Au flexible SERS substrate:
WO prepared in step 2 3-x Centrifuging and concentrating the Au-0.01 composite nanoparticle solution at 10000 rpm for 12 min, and taking WO with volume of 50 μl with a pipette 3-x Slowly dripping Au concentrated solution onto round filter paper with aperture of 0.2 μm and diameter of 0.8 cm, and air drying to obtain WO 3-x -Au flexible SERS substrate, stored for use.
Step 4, detection of rhodamine 6G:
5 μl of rhodamine 6G-containing solution (concentration 10 respectively -4 , 10 -5 , 10 -6 , 10 -7 , 10 -8 mol/L) is added dropwise to the WO prepared in step 3 3-x On an Au flexible SERS substrate, signal acquisition was performed using a portable raman spectrometer, with a laser wavelength of 785 nm, a scanning time of 15 s, and integration times of 1, to obtain a SERS spectrum of rhodamine 6G (fig. 2 (a)).
FIG. 1 is a diagram of WO prepared in example 1 of the present invention 3-x Sea urchin-like nanoparticles and WO 3-x -transmission electron micrographs of Au composite nanoparticles; wherein (a) is WO 3-x A low-power TEM image of sea urchin-like nanoparticles, (b) WO 3-x High-power TEM image of sea urchin-like nanoparticle, (c) is WO 3-x XRD spectrum of sea urchin-like nanoparticle, wherein (d) is WO 3-x -low-power TEM image of Au complex nanoparticle, (e) WO 3-x High-power TEM image of Au composite nanoparticles, (f) is WO 3-x XRD spectrum of Au composite nanoparticle.
FIG. 1 shows WO prepared in example 1 3-x The nano particles are of multi-thorn sea urchin structures, the average particle diameter is about 1.2 mu m, single thorns show good lattice structures, the lattice fringe spacing is 0.38 nm, and the combination of XRD results shows that the synthesized sea urchin-shaped WO 3-x The nanoparticle is WO 2.72 ；WO 3-x The Au composite nano-particles still show a echinoid structure, and XRD results show that WO 3-x The Au composite nano-particles are prepared from WO 2.72 And Au, wherein Au nano particles with lattice spacing of 0.24 nm are uniformly distributed on the surface of the single thornThe average particle diameter of the pellets was 3 nm.
FIG. 2 shows the WO of the invention prepared in example 1 at various concentrations of rhodamine 6G 3-x Raman spectrum of surface of Au flexible SERS substrate (a), logarithm of rhodamine 6G concentration and 1365 cm -1 A linear relationship (b) established by the raman peak intensities.
FIG. 2 fully illustrates the WO used in the present invention 3-x The Au flexible SERS substrate can enrich rhodamine 6G on the surface of the substrate and generate corresponding Raman enhancement effect, and the method comprises the following steps of 3-x The detection limit of the-Au flexible SERS substrate on rhodamine 6G is 10 -8 mol/L。
FIG. 3 is a diagram of WO prepared in example 1 of the present invention 3-x -homogeneity evaluation of rhodamine 6G detection by Au flexible SERS substrate; wherein (a) is the same WO 3-x Randomly selecting a Raman spectrum of 16 sample points on the surface of the Au flexible SERS substrate, wherein (b) rhodamine 6G is 1365 cm for the 16 sample points -1 At the raman peak intensity value.
FIG. 3 shows the WO thus prepared 3-x The Au flexible SERS substrate is stable in detection signals of rhodamine 6G, and the method has potential to be applied to actual sample detection.
FIG. 4 shows WO prepared in example 1 of the present invention 3-x -evaluation of anti-interference performance of Au flexible SERS substrate on rhodamine 6G detection.
FIG. 4 shows the results of the other dyes (rhodamine 6G concentration 2X 10) -5 mol/L, sunset yellow concentration of 2×10 -5 mol/L, methyl orange concentration of 2×10 -5 mol/L) are coexisted, WO is prepared 3-x The detection effect of the Au flexible SERS substrate on rhodamine 6G is not interfered, and the method has the potential of being applied to actual sample detection.
Comparative example 1
Au-WO 3 The preparation method of the composite material comprises the following steps:
s1, preparation of WO 3 Hollow ball:
s1.1, 0.30 g WCl 6 Adding the mixture into 40 mL glacial acetic acid, mechanically stirring and dissolving, performing solvothermal reaction at 180 ℃ for 12 h, and performing suction filtration, washing and drying after the reaction is finished;
s1.2 calcining the product obtained in S1.1 at 500 ℃ for 2 h to obtain WO 3 A hollow sphere; specific surface area of 25 cm 2 /g；
S2, preparation of Au-WO 3 Composite material:
s2.1 WO obtained by reacting S1 3 The hollow spheres were all immersed in absolute ethanol at 1.1 h and then HAuCl at 1.29 mL concentration of 1.1 mg/mL 4 · 3H 2 Adding O solution into the solution, soaking 4 h, and then carrying out suction filtration, washing and drying;
s2.2, calcining the product obtained in S2.1 at 300 ℃ to treat 1 h to obtain Au-WO 3 A composite material.
Results: au-WO prepared in this comparative example 3 The detection limit of the composite material on rhodamine 6G is 10 -6 mol/L, response signals are susceptible to interference from other co-existing dyes.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (1)
1. WO (WO) 3-x Application of Au flexible SERS substrate in detection of rhodamine 6G is characterized in that the WO 3-x The preparation method of the Au flexible SERS substrate comprises the following steps of;
step 1, WO 3-x Preparation of sea urchin-like nanoparticles:
weigh WCl 6 Adding the reagent 0.4 g into the liner of a 100 mL reaction kettle, adding 40 mL absolute ethyl alcohol, and magnetically stirring until WCl is obtained 6 Dissolving the powder until the solution becomes transparent and has no turbidity; transferring the inner container of the reaction kettle into the outer shell of the reaction kettle, putting into a drying oven, and setting the temperature to be 180 DEG C o C, heating time is set to be 12 h; after heating, naturally cooling the reaction kettle, centrifuging at 12000 rpm for 10 min, separating solid from liquid, collecting solid particles, repeatedly cleaning the solid collected after centrifuging with absolute ethyl alcohol for 5 times, and then placing in a vacuum drying oven for 60 times o Drying under C12-h, oven drying, grinding into powder with mortar to obtain WO 3-x Sea urchin-like nanoparticles;
step 2, WO 3-x -preparation of Au complex nanoparticle solution:
preparation of HAuCl at a concentration of 0.01% 4 ·4H 2 O solution, taking the formulated HAuCl 4 ·4H 2 O solution 15 and mL, and respectively weighing WO prepared in step 1 3-x Adding sea urchin-like nanoparticle 10 mg to the above HAuCl 4 ·4H 2 The mixed solution is obtained from the O solution by using a magnetic stirrer 25 o Stirring at 400 rpm at normal temperature for 5min until powder is dispersed; with continuous stirring, the irradiation intensity was 120 mw/cm 2 The mercury lamp irradiates the above WO 3-x And HAuCl 4 ·4H 2 Mixing the solution of O for 20 min; obtaining WO 3-x -Au complex nanoparticle solution;
step 3, WO 3-x -preparation of Au flexible SERS substrate:
WO prepared in step 2 3-x Centrifuging and concentrating the Au-0.01 composite nanoparticle solution at 10000 rpm for 12 min, and taking WO with volume of 50 μl with a pipette 3-x Slowly dripping Au concentrated solution onto round filter paper with aperture of 0.2 μm and diameter of 0.8 cm, and air drying to obtain WO 3-x -Au flexible SERS substrate.
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