CN110857914A - Poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate and preparation method thereof - Google Patents
Poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polytrifluoropropylmethylsiloxane/silver composite surface enhanced Raman substrate and a preparation method thereof. According to the method, a layer of silver nanoparticles with uniform particle size and dense arrangement is formed on the surface of a polytrifluoropropylmethylsiloxane membrane by utilizing the enrichment effect of polytrifluoropropylmethylsiloxane on nitrobenzene pollutants and combining a sol-gel method and an in-situ chemical reduction method, so that the polytrifluoropropylmethylsiloxane/silver composite surface enhanced Raman substrate is prepared. The polytrifluoropropylmethylsiloxane membrane in the composite surface enhanced Raman substrate has a good enrichment effect on nitro pollutants in water, does not cause any interference on measurement, has good repeatability, controllable process, high sensitivity and low cost, and can be used for surface enhanced Raman spectroscopy measurement of various substances.
Description
Technical Field
The invention belongs to the technical field of organic matter detection, and relates to a polytrifluoropropylmethylsiloxane/silver composite surface enhanced Raman substrate and a preparation method thereof.
Background
The surface enhanced Raman scattering spectroscopy (SERS) technology is widely applied to the fields of analytical chemistry, life science, medicine and the like, and has the characteristics of quick response, accuracy, sensitivity, no damage to samples and the like. The method needs to utilize coinage metals such as Au, Ag, Cu and the like to prepare the surface enhanced Raman substrate with a rough surface, wherein the effect of the Ag substrate is optimal.
The nano silver particles are generally applied to the preparation of the surface enhanced Raman spectrum substrate due to the characteristics of high surface activity and the like, but the factors such as the size, the spacing, the arrangement and the like of the nano silver particles can have great influence on the effect of the substrate. Since the prepared silver nanoparticles are easy to oxidize and can affect the Raman effect of the substrate, the oxidation process of the silver nanoparticles is slowed down by composite coating of silicon dioxide and the like (M.Shanthil, Hemna Fathima, and K.George Thomas.cost-Effective plasma substrates: glass Capillaries purified with Ag @ SiO;)2Nanoparticies on Inner Walls Walls as SERSSubstrates ACS appl. Mater. interfaces,2017,9(23), 19470-. In addition, the flexible material is also commonly used for loading nano silver particles, so that a complex 3D structure can be utilized, the loading points of the silver nanoparticles are increased, and a high-density Raman 'hot spot' is formed (Liyi, silver nanoparticle modified electrostatic spinning flexible poly (bisphenol A carbonate) nanofiber is used as an effective 3D SERS substrate for trace TNT detection, analystt, 2017,142,4756).
Disclosure of Invention
The invention aims to provide a rapid, simple and convenient poly (trifluoropropylmethylsiloxane)/silver composite surface-enhanced Raman substrate which is excellent in enhancement effect and is not influenced by nitrobenzene pollutants and a preparation method thereof. According to the method, a layer of silver nanoparticles with uniform particle size and dense arrangement is formed on the surface of a polytrifluoropropylmethylsiloxane membrane by utilizing the enrichment effect of polytrifluoropropylmethylsiloxane on nitrobenzene pollutants and combining a sol-gel method and an in-situ chemical reduction method, so that the polytrifluoropropylmethylsiloxane/silver composite surface enhanced Raman substrate is prepared.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the poly (trifluoropropylmethylsiloxane)/silver composite surface-enhanced Raman scattering substrate comprises the following steps of forming a poly (trifluoropropylmethylsiloxane) film on the surface of a substrate by using a sol-gel technology, reducing silver nitrate into uniform silver nanoparticles by using a chemical reduction method, and finally obtaining the poly (trifluoropropylmethylsiloxane)/silver composite surface-enhanced Raman scattering substrate by self-assembly, wherein the preparation method comprises the following specific steps:
step 1, adding a 95% trifluoroacetic acid solution into methyltrimethoxysilane, oscillating, uniformly mixing, adding polytrifluoropropylmethylsiloxane, oscillating, uniformly mixing, dropwise adding onto a glass sheet, and naturally air-drying to obtain a polytrifluoropropylmethylsiloxane film;
and 2, immersing the poly (trifluoropropyl methyl siloxane) film into the silver nanoparticle solution, taking out, and air-drying to obtain the poly (trifluoropropyl methyl siloxane)/silver composite surface-enhanced Raman substrate, wherein the mass ratio of the silver nanoparticles to the poly (trifluoropropyl methyl siloxane) is 1: 20-1: 4.
Further, in step 1, the glass sheet is subjected to activation pretreatment by concentrated sulfuric acid, sodium hydroxide and hydrochloric acid.
Further, in the step 1, the mass ratio of the methyltrimethoxysilane to the polytrifluoropropylmethylsiloxane is 1.5: 1-1.2: 1.
Further, in the step 2, the concentration of the silver nanoparticle solution is 0.2-0.4 mM.
Compared with the prior art, the invention has the following advantages:
(1) the preparation process is simple and convenient, and large instruments and complex sample pretreatment are not needed;
(2) compared with the traditional test environment (in gaseous pollutants), the polytrifluoropropylmethylsiloxane membrane in the composite surface enhanced Raman substrate has a good enrichment effect on nitrate pollutants in water, does not cause any interference on measurement, has good repeatability, controllable process, high sensitivity and low cost, and can be used for surface enhanced Raman spectroscopy measurement of various substances;
(3) the content of the silver nanoparticles on the polytrifluoropropylmethylsiloxane membrane can be adjusted through the concentration of the silver nanoparticles, and the quantity of 'hot spots' can be ensured by the loaded silver particles, so that the maximum SERS enhancement of nitro pollutants is realized.
Drawings
FIG. 1 is a graph showing the adsorption curves of the polytrifluoropropylmethylsiloxane membranes prepared in example 1 for various concentrations of nitrobenzene.
FIG. 2 shows poly (trifluoropropylmethylsiloxane)/silver composite surface-enhanced Raman substrate pairs 10 prepared in example 2 under different concentrations of silver nanoparticles-7Raman spectrum of M concentration probe molecule (4-mercaptoaniline) (a.0.2mM; b.0.4mM; c.0.6 mM; d.0.8mM; e.1.0 mM).
FIG. 3 shows the poly (trifluoropropylmethylsiloxane)/silver composite surface-enhanced Raman substrate pair 10 prepared in example 2 under different concentrations of silver nanoparticles-7M concentration of the probe molecule (4-mercaptoaniline) at 1436cm-1The Raman intensity of the silver nanoparticles is plotted as a function of the concentration of the silver nanoparticles.
FIG. 4 is a scanning electron micrograph of the self-assembly of different concentrations of Ag nanoparticles prepared in example 2 on a polytrifluoropropylmethylsiloxane membrane (a.0.2mM; b.0.4 mM; c.0.6 mM; d.0.8 mM; e.1.0 mM).
FIG. 5 is a comparative identification chart of Raman spectra of the poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate p-nitrobenzene prepared in example 3.
FIG. 6 is a Raman spectrum of the poly (trifluoropropylmethylsiloxane)/silver composite surface-enhanced Raman substrate prepared in example 3 for different concentrations of nitrobenzene (a.1000mg/L; b.40mg/L; c.10 mg/L; d.1 mg/L).
Detailed Description
The present invention is further described with reference to the following specific examples and accompanying drawings, but should not be construed as limiting the scope of the invention. Any insubstantial modifications or adaptations of the invention from the foregoing disclosure by those skilled in the art are intended to be covered by the present invention.
Example 1
(1) Cleaning glass sheets, soaking in concentrated sulfuric acid for 3h, cleaning with distilled water, soaking in 1M NaOH for 2h, cleaning with distilled water, soaking in 0.1M HCl for 30min, cleaning with distilled water, and oven drying at 120 deg.C overnight;
(2) adding 3g of methyltrimethoxysilane into 2mL of trifluoroacetic acid (containing 5% of water), shaking and mixing uniformly for 1h, adding 2.5g of polytrifluoropropylmethylsiloxane, shaking and mixing uniformly, dropping 100 mu L of mixed solution on a glass sheet by using a liquid transfer gun, and naturally drying to form a film;
(3) placing the membrane in the step (2) in nitrobenzene solutions with different concentrations for constant temperature oscillation, measuring absorbance by using an ultraviolet spectrophotometry after the adsorption reaches the balance, and calculating the adsorption quantity of the poly (trifluoropropylmethylsiloxane) membrane to the nitrobenzene by using a formula:
in the formula, CiIs the initial concentration of nitrobenzene (mg/L), CfIs the concentration of nitrobenzene (mg/L) after a certain period of adsorption, V is the volume of nitrobenzene solution (L), and m is the mass of the polytrifluoropropylmethylsiloxane membrane (g).
FIG. 1 is an adsorption curve of the poly (trifluoropropylmethylsiloxane) membrane prepared in example 1 on nitrobenzene with different concentrations, and it can be seen that the concentration of nitrobenzene and the adsorption amount present a certain linear relationship, and the adsorption amount of the poly (trifluoropropylmethylsiloxane) membrane on nitrobenzene increases with the increase of the concentration of nitrobenzene, and the adsorption amount can be as high as 12mg/g when the concentration of nitrobenzene is 100 mg/L.
Example 2
(1) And (2) soaking the poly (trifluoropropylmethylsiloxane) obtained in the example 1 in silver nanoparticle solutions with different concentrations for 24h to obtain the poly (trifluoropropylmethylsiloxane)/silver composite surface-enhanced Raman substrate with different silver contents.
(2) The obtained poly (trifluoropropylmethylsiloxane)/silver composite surface reinforcing steelThe man substrate is immersed at 10-7And (3) obtaining a corresponding surface enhanced Raman spectrum in the probe molecule (4-mercaptoaniline) solution with the concentration of M.
The poly (trifluoropropylmethylsiloxane)/silver composite surface-enhanced Raman substrate pair 10 prepared from the silver nanoparticles with different concentrations-7The Raman spectrum of the M-concentration probe molecule (4-mercaptoaniline) is shown in FIG. 2 (a.0.2 mM; b.0.4 mM; c.0.6 mM; d.0.8 mM; e.1.0mM), and it can be seen that the Raman spectrum intensity of the probe molecule gradually decreases as the concentration of Ag nanoparticles increases. Wherein, the 4-mercaptoaniline is 1436cm-1The change relationship of the Raman intensity of the Ag nanoparticles with different concentrations is shown in FIG. 3, and it can be seen that the Ag nanoparticles have excellent surface enhanced Raman effect at the concentration of 0.2-0.4 mM.
The scanning electron micrograph of the self-assembly of Ag nanoparticles with different concentrations on the polytrifluoropropylmethylsiloxane membrane is shown in FIG. 4 (a.0.2mM, b.0.4mM, c.0.6mM, d.0.8mM, e.1.0mM), and it can be seen that the amount of Ag nanoparticles adsorbed on the prepared polytrifluoropropylmethylsiloxane membrane increases with the increase of the concentration of Ag nanoparticles, and the Raman spectrum intensity is greatly influenced by the concentration of Ag nanoparticles, and if the concentration of Ag nanoparticles is too high, the particles are agglomerated, and the Raman enhancement effect is rather weakened, therefore, the scanning electron micrograph of FIG. 4 is consistent with the result of FIG. 2.
Example 3
(1) And (3) soaking the polytrifluoropropylmethylsiloxane obtained in the example 1 in a silver nanoparticle solution with the concentration of 0.2mM for 24h to obtain the polytrifluoropropylmethylsiloxane/silver composite surface enhanced Raman substrate.
(2) And immersing the obtained poly (trifluoropropyl methyl siloxane)/silver composite surface enhanced Raman substrate in nitrobenzene solutions with different concentrations to obtain corresponding surface enhanced Raman spectra.
The Raman contrast confirmation spectrogram of the prepared poly (trifluoropropylmethylsiloxane)/silver composite surface-enhanced Raman substrate for pure nitrobenzene is shown in figure 5, and the prepared poly (trifluoropropylmethylsiloxane)/poly (trifluoropropylmethylsiloxane) membrane + pure nitrobenzene, silver nanoparticles + pure nitrobenzene, and poly (trifluoropropylmethylsiloxane) are respectively shown in figure 5The Raman detection is carried out on the alkane/silver composite surface enhanced Raman substrate and pure nitrobenzene, so that the Raman spectrogram of the nitrobenzene can not be detected no matter the single polytrifluoropropylmethylsiloxane membrane or the single silver nanoparticle p-nitrobenzene is adopted, and the Raman spectral characteristic peaks of the nitrobenzene can be detected by compounding the two substances, wherein the characteristic peaks are 864cm respectively-1、1005cm-1、1109cm-1、1347cm-1、1590cm-1。
The Raman spectra of a series of nitrobenzene with different concentrations are shown in FIG. 6 (a.1000mg/L, b.40mg/L, c.10mg/L, d.1mg/L), which is 1590cm with the decrease of nitrobenzene concentration-1The peak intensity of C ═ C aromatic stretching vibration is reduced, and when the concentration of nitrobenzene is lower than 10mg/L, no peak can be produced, so that the minimum detection concentration of the poly (trifluoropropylmethylsiloxane)/silver composite surface enhanced Raman substrate p-nitrobenzene is 10 mg/L.
Claims (5)
1. The preparation method of the polytrifluoropropylmethylsiloxane/silver composite surface enhanced Raman substrate is characterized by comprising the following specific steps:
step 1, adding a 95% trifluoroacetic acid solution into methyltrimethoxysilane, oscillating, uniformly mixing, adding polytrifluoropropylmethylsiloxane, oscillating, uniformly mixing, dropwise adding onto a glass sheet, and naturally air-drying to obtain a polytrifluoropropylmethylsiloxane film;
and 2, immersing the poly (trifluoropropyl methyl siloxane) film into the silver nanoparticle solution, taking out, and air-drying to obtain the poly (trifluoropropyl methyl siloxane)/silver composite surface-enhanced Raman substrate, wherein the mass ratio of the nanoparticles to the poly (trifluoropropyl methyl siloxane) is 1: 20-1: 4.
2. The method according to claim 1, wherein in step 1, the glass sheet is subjected to an activation pretreatment with concentrated sulfuric acid, sodium hydroxide and hydrochloric acid.
3. The preparation method according to claim 1, wherein in the step 1, the mass ratio of the methyltrimethoxysilane to the polytrifluoropropylmethylsiloxane is 1.5: 1-1.2: 1.
4. The method according to claim 1, wherein the concentration of the silver nanoparticle solution in step 2 is 0.2 to 0.4 mM.
5. The polytrifluoropropylmethylsiloxane/silver composite surface enhanced Raman substrate prepared by the preparation method according to any one of claims 1 to 4.
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