CN111196680A - Silver-tungsten trioxide nano composite material, preparation method and application thereof - Google Patents
Silver-tungsten trioxide nano composite material, preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a silver-tungsten trioxide nano composite material, a preparation method and an application thereof, and belongs to the technical field of material chemistry. The method comprises the preparation of tungsten trioxide nanosheets, the preparation of in-situ grown silver-tungsten trioxide nanosheets, the testing of surface enhanced Raman scattering properties of the silver-tungsten trioxide nanosheets and the detection of dye molecule rhodamine 6G (R6G) by using a silver-tungsten trioxide nanosheet substrate. The silver-tungsten trioxide nanosheet prepared on the FTO conductive glass has good uniformity and stability, and shows excellent surface enhanced Raman scattering property, and the lowest detection of the dye R6G can reach 10‑11mol/L。
Description
Technical Field
The invention relates to the technical field of laser Raman detection and the field of nano-materials science, in particular to a silver-tungsten trioxide nano-composite material, a preparation method and application thereof.
Background
The Surface Enhanced Raman Scattering (SERS) effect is found in the mid-seventies of the last century, and has attracted great interest to scientists due to its special adsorption effect and rapidly found wide application in various scientific fields. In recent years, oxide surface modification materials have been the focus of research for improving the properties of nanomaterials. The silver nanoparticles are favored by people due to good electro-catalytic performance and biocompatibility, and compared with other metal particles, the silver nanoparticles can enhance the electromagnetic field (106-1010 times) near the particles due to the strong surface plasmon resonance effect. Based on this property, the surface enhanced raman effect of silver nanoparticles is better.
Researches show that the surface enhanced raman scattering technology of transition metal oxides such as tungsten oxide nano materials can greatly expand the research of SERS, and simultaneously the SERS research of metal-metal oxide nano composite systems has made certain progress, such as spraying gold nanoparticles to titanium dioxide nanosheet structures (j.mater.chem., 2012,22, 856), growing silver nanoparticles on titanium dioxide rods (j.mater.chem., 2011,21, 10189), tin oxide nanospheres and nanocubes, and the like (j.phys.chem.c. 2011,115, 18378). These materials combine noble metals with semiconductor oxides, combining the excellent properties of semiconductors and noble metals, making the semiconductor-noble metal structures also have very good optical properties.
Disclosure of Invention
The invention aims to provide a silver-tungsten trioxide nano composite material which is simple in preparation method, uniform in substrate and high in sensitivity, can be used for high-sensitivity Raman detection, and also provides a preparation method of the material and application of the material in SERS signal detection.
In the silver-tungsten trioxide nano composite material prepared by the invention, the tungsten trioxide is prepared by uniformly coating tungstic acid seed liquid on the surface of FTO conductive glass, and carrying out hydrothermal reaction, high-temperature annealing and other steps.
A preparation method of a silver-tungsten trioxide nano composite material comprises the following steps:
(1) preparation of substrate covered with tungstic acid seed liquid
Adding tungstic acid and polyvinyl alcohol into a hydrogen peroxide solution, stirring and dissolving to obtain a milky solution to obtain a seed solution, uniformly covering the seed solution on the surface of conductive glass by a spin coating method, uniformly heating the conductive glass covered with the seed solution to 450-550 ℃, keeping the temperature for 1-3 hours, and naturally cooling to room temperature to obtain a substrate used in the next experiment;
(2) uniformly mixing a hydrogen peroxide solution of tungstic acid, oxalic acid, urea, hydrochloric acid and acetonitrile to obtain a hydrothermal reaction solution; placing the substrate prepared in the step (1) in a hydrothermal reaction solution, reacting for 1-3 h at 150-200 ℃, naturally cooling to room temperature, taking out, cleaning and drying;
(3) calcining the sample piece subjected to hydrothermal reaction in the step (2) in a hydrogen atmosphere at 300-500 ℃ for 2-4 hours, and naturally cooling to room temperature to obtain a tungsten trioxide nanosheet sample growing on the conductive glass;
(4) cutting the prepared tungsten trioxide nanosheet sample growing on the conductive glass into sample pieces, placing the sample pieces at the bottom of a beaker, and adding 0.1-0.8mol/L AgNO3And stirring the solution for 2-8h in the dark, taking out a sample piece, washing, drying, and placing in a vacuum drying oven for later use.
Further, in the step (1), the mass ratio of the tungstic acid to the polyvinyl alcohol is 5:2, the concentration of the hydrogen peroxide solution is 30wt%, 13.6mL of 30wt% hydrogen peroxide solution is needed for each 1g of tungstic acid, 100 mu L of seed solution is dropwise added each time, and the steps are repeated for 6-8 times.
Further, the preparation process of the hydrogen peroxide solution of tungstic acid in the step (2) is as follows: adding tungstic acid and 30wt% hydrogen peroxide into water respectively, stirring at 90-100 ℃ until the tungstic acid and the 30wt% hydrogen peroxide are dissolved, and cooling to room temperature to obtain the tungstic acid/1 g tungstic acid which needs 13.6mL of 30wt% hydrogen peroxide solution and 67mL of water.
Further, 13.6mL of 30wt% hydrogen peroxide solution per 1g of tungstic acid, 0.02g of oxalic acid, 0.02g of urea, 0.5mL of 4-6mol/L of hydrochloric acid, and 12.5mL of acetonitrile per 3mL of tungstic acid in hydrogen peroxide solution were required.
Further, the size of the sample piece in the step (4) is 1cm x 1cm, the sample piece is placed at the bottom of the beaker, and 5mL of AgNO with the concentration of 0.1mol/L to 0.8mol/L is added into the sample piece3And (3) solution.
Specifically, the tungstic acid seed liquid is prepared by adding 2.5g of tungstic acid and 1.0g of polyvinyl alcohol into 34mL of hydrogen peroxide solution with the mass fraction of 30%, stirring and dissolving at room temperature to finally form a milky uniform solution. Putting the cleaned and dried FTO conductive glass with the conductive surface facing upwards on a spin coater, dripping 100 mu L of seed liquid on the conductive glass every time at the spin coating speed of 3000-5000rpm for 30 seconds, repeating the operation for 6-8 times, then putting the sample piece in an air atmosphere, raising the temperature to 500 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and then naturally cooling to room temperature. And obtaining the FTO conductive glass sample piece coated with the tungstic acid seed liquid.
The hydrothermal reaction is prepared by respectively adding 3mL of tungstic acid solution, 0.02g of oxalic acid, 0.02g of urea and 0.5mL of hydrochloric acid (4-6 mol/L) into 12.5mL of acetonitrile solution and uniformly mixing. Thus obtaining the hydrothermal reaction solution. Transferring the hydrothermal reaction solution into a liner of a reaction kettle, inserting the prepared FTO conductive glass sample piece coated with the tungstic acid seed solution into the hydrothermal reaction solution, and reacting for 2 hours at the temperature of 180 ℃. After cooling to room temperature, the sample piece was taken out, washed clean with clear water and dried with nitrogen. And (5) standby.
The tungstic acid solution in the hydrothermal reaction was prepared by adding 1g of tungstic acid and 13.6mL of hydrogen peroxide (mass fraction: 30%) to 67mL of water, respectively, stirring to dissolve at 95 deg.C, and cooling to room temperature. Thus obtaining the tungstic acid solution used in the experiment.
The preparation of the high-temperature annealing reaction is that a sample sheet prepared after the hydrothermal reaction is placed in a muffle furnace, air is introduced for 30 minutes at the flow rate of 50mL/min under the hydrogen atmosphere, then the temperature is raised to 500 ℃ at the speed of 10 ℃/min, the temperature is kept for 2-4 hours, and then the sample is naturally cooled to the room temperature, so that the tungsten trioxide nanosheet sample growing on the FTO conductive glass is obtained.
Cutting the prepared tungsten trioxide nanosheet sample growing on the FTO conductive glass into sample pieces with the size of 1 × 1cm, placing the sample pieces at the bottom of a beaker, adding 5mL of 0.1-0.8mol/L AgNO3 solution, stirring for 2-8h in a dark place, taking out the sample pieces, repeatedly washing for 3-5 times by using ultrapure water, drying by using nitrogen, and placing the sample pieces in a vacuum drying box for later use.
Application of silver-tungsten trioxide nanocomposite to surface-enhanced Raman scattering base material in detection of rhodamine 6G (R6G), wherein 50 mu L of R6G solution is dropwise added onto the base material, and the lowest detection concentration is 10-11mol/L。
The silver-tungsten trioxide nano composite material is applied to SERS detection, and the detection of R6G is carried out by enhancing the mutual electromagnetic field of noble metal and semiconductor oxide to realize surface-enhanced Raman scattering.
According to the invention, the nano-sheet of tungsten trioxide uniformly grown on FTO conductive glass is prepared by a seed coating method and a hydrothermal method, and the silver nano-particles uniformly grown on the surface of the tungsten trioxide nano-sheet, namely the silver-tungsten trioxide nano composite material, are prepared by an in-situ growth method through the reducibility expressed by the tungsten trioxide. The in-situ growth method adopted by the invention can obtain the nano composite material with the metal-oxide structure under the condition of stirring tungsten trioxide and silver nitrate at room temperature without using a reducing agent, and the material can be used as a Raman enhanced substrate and chemical molecule analysis detection.
The silver-tungsten trioxide nano composite material prepared by the invention shows good performanceThe surface enhances the properties of raman scattering. The lowest detection for dye rhodamine 6G can reach 10-11mol/L. The nano structure has good application prospect in the field of sensing detection.
Drawings
FIG. 1 is a scanning electron microscope image of silver-tungsten trioxide nanocomposite at different magnifications: (a) 2 ten thousand times of amplification, (b) 10 ten thousand times of amplification;
FIG. 2 is a transmission single photon microscope image of a silver-tungsten trioxide nanocomposite material;
FIG. 3 is an X-ray photoelectron spectrum of a silver-tungsten trioxide composite;
FIG. 4 is a Raman spectrum of rhodamine 6G at different concentrations;
FIG. 5 shows the concentration of rhodamine 6G and 1365cm-1Standard plot of raman intensity at (a).
Detailed Description
The technical solution of the present invention is further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
The FTO conductive glass used in the experiment is ultrasonically cleaned for twenty minutes by ethanol, acetone and water respectively before use, and then is dried by nitrogen for later use. The water used in the experiment was 18.2 M.OMEGA.ultrapure water.
A preparation method of a silver-tungsten trioxide nano composite material comprises the following specific steps:
1. preparation of FTO sample piece coated with tungstic acid seed liquid on surface
Adding 2.5g of tungstic acid and 1.0g of polyvinyl alcohol into 34mL of hydrogen peroxide solution with the mass fraction of 30%, stirring and dissolving at room temperature to finally form milky uniform solution. Putting the cleaned and dried FTO conductive glass with the conductive surface facing upwards on a spin coater, dripping 100uL of seed liquid on the conductive glass every time at the speed of 3000rpm for 30 seconds, repeating the operation for 6-8 times, putting the sample piece in an air atmosphere, raising the temperature to 500 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and naturally cooling to room temperature. Thus obtaining the FTO conductive glass sample piece coated with the seed liquid.
2. Preparation of hydrothermal reaction solution
1g of tungstic acid and 13.6mL of hydrogen peroxide (30 percent by mass) are respectively added into 67mL of water, stirred to be dissolved at the temperature of 95 ℃, and cooled to room temperature, thus obtaining the tungstic acid solution used in the experiment.
3mL of tungstic acid solution, 0.02g of oxalic acid, 0.02g of urea and 0.5mL of 6mol/L hydrochloric acid are respectively added into 12.5mL of acetonitrile solution and mixed evenly. Thus obtaining the hydrothermal reaction solution. Transferring the hydrothermal reaction solution into a liner of a reaction kettle, inserting the sample piece prepared in the step (1) into the hydrothermal reaction solution, and reacting for 2 hours at 180 ℃. After cooling to room temperature, the sample piece was taken out, washed clean with clear water and dried with nitrogen. And (5) standby.
3. Preparation of tungsten trioxide nanosheet growing on FTO substrate
And (3) putting the sample piece prepared in the step (2) into a muffle furnace, ventilating for 30 minutes at the flow rate of 50mL/min in the hydrogen atmosphere, heating to 450 ℃ at the speed of 10 ℃/min, keeping for 4 hours, and naturally cooling to room temperature to obtain the tungsten trioxide nanosheet sample growing on the FTO conductive glass.
4. Preparation of silver-tungsten trioxide nano composite material grown on FTO substrate
Cutting a tungsten trioxide nanosheet sample grown on FTO conductive glass into sample pieces with the size of 1cm x 1cm, placing the sample pieces at the bottom of a beaker, adding 5mL of AgNO with the concentration of 1mol/L, 0.2 mol/L and 0.4mol/L into the sample pieces3Stirring the solution for 5h in dark place, taking out a sample piece, repeatedly washing with ultrapure water for 3-5 times, drying with nitrogen, storing in a normal-temperature vacuum drying oven, and adding 0.4mol/LAgNO3The prepared samples were used for subsequent testing of surface enhanced raman scattering properties.
The substrate after nitrogen blow-drying is detected, as shown in fig. 1, a scanning electron microscope image of the prepared silver-tungsten trioxide nanocomposite (a) is a nano composite structure under the magnification of 2 ten thousand times, and it can be seen that the prepared nanosheets are relatively uniform, but due to the small magnification, the prepared silver growing on the surface of tungsten trioxide is not clear under the low magnification due to the small particle size. (b) The scanning electron microscope image of the graph under 10 ten thousand times of magnification clearly shows that some silver nanoparticles grow on the surface of the tungsten trioxide nanosheet. It is shown that the silver-tungsten trioxide nanocomposite can be prepared by an in-situ growth method. Fig. 2 is a transmission electron microscope image of the prepared silver-tungsten trioxide nanocomposite, and it can be clearly seen from fig. 2 that silver nanoparticles are formed on the surface of tungsten trioxide. The prepared silver-tungsten trioxide nanosheet is subjected to X-ray photoelectron spectroscopy analysis, and characteristic peaks of Ag, O and W, namely Ag (367.31 eV), O (530.2 eV) and W (35.31 eV), are clearly seen on a spectrogram in FIG. 3. Indicating the presence of silver after in situ growth, which is consistent with the results of the transmission and scanning electron micrographs tested.
5, using the silver-tungsten trioxide nano composite material for detecting the R6G dye
Preparing six R6G aqueous solutions with different concentrations of 10-6mol/L，10-7mol/L，10-8mol/L，10-9mol/L，10-10mol/L，10-11And (3) mol/L, taking 6 prepared silver-tungsten trioxide nano composite materials with the size of 1cm x 1cm growing on FTO conductive glass as an SERS substrate. On this substrate, 50. mu.L of R6G solutions of different concentrations were dropped, and left to dry at room temperature. The parameters of the Raman test are respectively 633nm of laser, 25 percent of optical filter, 3 times of test and 200cm of Raman shift-1-2000cm-1. Namely obtaining the Raman spectrogram of R6G taking the silver-tungsten trioxide nano composite material as the Raman substrate under different concentrations, and the specific result is shown in figure 4.
Drawing of standard curve of R6G detection
As can be seen from FIG. 4, the molecule R6G is at 1365cm-1Has the highest peak value and obvious peak shape, and the Raman peak can be attributed to the peak generated by C-C bond stretching vibration on the R6G molecule, so that the Raman is shifted by 1365cm-1The peak of (a) was taken as a characteristic peak of R6G. Taking the Raman shift at 1365cm-1The peak value of the characteristic peak of the R6G molecule was plotted on the abscissa as the logarithm of the concentration,and the Raman characteristic peak intensity is plotted as an ordinate by using origin8.5, namely a standard curve chart of the detection of R6G is obtained, and the specific result is shown in a figure 5.
The prepared silver-tungsten trioxide nanosheets growing on the surface are used as a substrate for surface enhanced Raman scattering, and R6G dyes with different concentrations are tested. As shown in fig. 4, it can be seen that as the concentration of R6G increases, the corresponding raman intensity also increases. At the same time, at 1365cm-1The Raman shift is a characteristic peak of R6G. And at 1365cm-1The raman intensity of (a) is plotted on the ordinate and the logarithm of the concentration of R6G is plotted on the abscissa, and the standard curve equation is that the raman intensity =3387.35 × lg (concentration) +40331.0889, R2=0.983, as shown in fig. 5, in the concentration range 10 of R6G-6mol/L-10-11In the mol/L range, a good linear relation is shown, and the detection limit is 1.72 x 10-12mol/L. The prepared silver-tungsten trioxide nanosheet is proved to have surface enhanced Raman scattering property, and can be well applied to dye detection.
Claims (9)
1. The preparation method of the silver-tungsten trioxide nano composite material is characterized by comprising the following steps:
(1) preparation of substrate covered with tungstic acid seed liquid
Adding tungstic acid and polyvinyl alcohol into a hydrogen peroxide solution, stirring and dissolving to obtain a milky solution to obtain a seed solution, uniformly covering the seed solution on the surface of conductive glass by a spin coating method, uniformly heating the conductive glass covered with the seed solution to 450-550 ℃, keeping the temperature for 1-3 hours, and naturally cooling to room temperature to obtain a substrate used in the next experiment;
(2) uniformly mixing a hydrogen peroxide solution of tungstic acid, oxalic acid, urea, hydrochloric acid and acetonitrile to obtain a hydrothermal reaction solution; placing the substrate prepared in the step (1) in a hydrothermal reaction solution, reacting for 1-3 h at 150-200 ℃, naturally cooling to room temperature, taking out, cleaning and drying;
(3) calcining the sample piece subjected to hydrothermal reaction in the step (2) in a hydrogen atmosphere at 300-500 ℃ for 2-4 hours, and naturally cooling to room temperature to obtain a tungsten trioxide nanosheet sample growing on the conductive glass;
(4) cutting the prepared tungsten trioxide nanosheet sample growing on the conductive glass into sample pieces, placing the sample pieces at the bottom of a beaker, and adding 0.1-0.8mol/L AgNO3And stirring the solution for 2-8h in the dark, taking out a sample piece, washing, drying, and placing in a vacuum drying oven for later use.
2. The preparation method of the silver-tungsten trioxide nanocomposite material as claimed in claim 1, wherein in the step (1), the mass ratio of the tungstic acid to the polyvinyl alcohol is 5:2, the concentration of the hydrogen peroxide solution is 30wt%, 13.6mL of 30wt% hydrogen peroxide solution is required for each 1g of tungstic acid, 100 μ L of seed solution is dropwise added each time, and the steps are repeated for 6-8 times.
3. The preparation method of the silver-tungsten trioxide nanocomposite material as claimed in claim 1, wherein the preparation process of the hydrogen peroxide solution of tungstic acid in the step (2) is as follows: adding tungstic acid and 30wt% hydrogen peroxide into water respectively, stirring at 90-100 ℃ until the tungstic acid and the 30wt% hydrogen peroxide are dissolved, and cooling to room temperature to obtain the tungstic acid/1 g tungstic acid which needs 13.6mL of 30wt% hydrogen peroxide solution and 67mL of water.
4. The method for preparing silver-tungsten trioxide nanocomposite as claimed in claim 1, wherein 0.02g of oxalic acid, 0.02g of urea, 0.5mL of 4-6mol/L of hydrochloric acid, 12.5mL of acetonitrile are required per 3mL of tungstic acid in hydrogen peroxide.
5. The method for preparing silver-tungsten trioxide nanocomposite material according to claim 1, wherein the size of the sample piece in the step (4) is 1cm x 1cm, the sample piece is placed on the bottom of a beaker, and 5mL of 0.1mol/L to 0.8mol/L AgNO is added thereto3And (3) solution.
6. A silver-tungsten trioxide nanocomposite produced by the production method according to any one of claims 1 to 5.
7. The use of the silver-tungsten trioxide nanocomposite material of claim 6 in SERS signal detection.
8. The use according to claim 7, for detecting the SERS signal of rhodamine 6G dye.
9. The application of the method as claimed in claim 8, wherein a silver-tungsten trioxide substrate material on conductive glass is used as a SERS substrate, a rhodamine 6G solution to be detected is dripped on the SERS substrate, and after drying, a Raman spectrometer is used for detecting a Raman scattering signal of the rhodamine 6G solution.
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| CN111804310A (en) * | 2020-07-23 | 2020-10-23 | 济南大学 | Preparation method of silver-tungsten trioxide-ferronickel layered double hydroxide composite material |
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| CN103708559A (en) * | 2013-12-19 | 2014-04-09 | 天津大学 | Tungsten trioxide nano-film with photocatalytic performance, and preparation method thereof |
| CN106525811A (en) * | 2016-10-14 | 2017-03-22 | 西安交通大学 | Dandelion-like Ag/WO3-x micro-nanostructured composite material-based SERS substrate, and preparation method and application thereof |
| CN107400899A (en) * | 2017-08-10 | 2017-11-28 | 黄河科技学院 | Tungstic acid complex light electrode and preparation method thereof and the application in photoelectrocatalysis decomposition water |
| CN108103525A (en) * | 2017-12-25 | 2018-06-01 | 黄河科技学院 | N doping carbon dots modification tungstic acid complex light electrode and preparation method thereof and the application in photoelectrocatalysis decomposes water |
| JP2018146410A (en) * | 2017-03-06 | 2018-09-20 | 国立研究開発法人物質・材料研究機構 | Three-dimensional Raman spectroscopy |
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| CN103708559A (en) * | 2013-12-19 | 2014-04-09 | 天津大学 | Tungsten trioxide nano-film with photocatalytic performance, and preparation method thereof |
| CN106525811A (en) * | 2016-10-14 | 2017-03-22 | 西安交通大学 | Dandelion-like Ag/WO3-x micro-nanostructured composite material-based SERS substrate, and preparation method and application thereof |
| JP2018146410A (en) * | 2017-03-06 | 2018-09-20 | 国立研究開発法人物質・材料研究機構 | Three-dimensional Raman spectroscopy |
| CN107400899A (en) * | 2017-08-10 | 2017-11-28 | 黄河科技学院 | Tungstic acid complex light electrode and preparation method thereof and the application in photoelectrocatalysis decomposition water |
| CN108103525A (en) * | 2017-12-25 | 2018-06-01 | 黄河科技学院 | N doping carbon dots modification tungstic acid complex light electrode and preparation method thereof and the application in photoelectrocatalysis decomposes water |
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| CN111804310A (en) * | 2020-07-23 | 2020-10-23 | 济南大学 | Preparation method of silver-tungsten trioxide-ferronickel layered double hydroxide composite material |
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