CN114199773A - Silver-plated optical fiber Raman probe and preparation method and application thereof - Google Patents
Silver-plated optical fiber Raman probe and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of material, optics and environment detection, in particular to a silver-plated optical fiber Raman probe, a preparation method and application thereof. The silver-plated optical fiber Raman probe provided by the invention realizes Cr (VI) ultrasensitive detection and excellent oxidation resistance by adopting methimazole functionalization. The preparation method provided by the invention has the advantages of simple process, high sensitivity, good repeatability, good stability and good anti-interference performance, and realizes the shape regulation of the silver nanoparticles on the end face of the optical fiber and the strong interface adhesion of the optical fiber and the silver nano material by adopting a stannous chloride-assisted solvothermal method. Specifically, the stannous chloride pretreatment process promotes the silver nanoparticles on the end face of the optical fiber to grow compactly and uniformly on the one hand, and enhances the interface adhesion between the optical fiber and the silver nanoparticles on the other hand. By adopting methimazole functionalization, Cr (VI) ultrasensitive detection and excellent oxidation resistance are realized.
Description
Technical Field
The invention relates to the field of material, optics and environment detection, in particular to a silver-plated optical fiber Raman probe and a preparation method and application thereof.
Background
Hexavalent chromium ions, as a major environmental pollutant, have high carcinogenicity and high mutagenicity. In recent years, detection equipment for hexavalent chromium ions in water is expensive, sample pretreatment is complex, and a test process is long, so that the development of a quick, high-sensitivity and low-cost biological detection technology is urgent. Compared with common ICP-OES and other detection technologies, SERS has the advantages of rapid detection, high nondestructive sensitivity and good specificity, and can be used in the field of environmental detection. The SERS technology is combined with the optical fiber, so that high-sensitivity flexible, real-time, in-situ, remote and low-loss detection can be realized, and the method has outstanding advantages in actual water body detection.
In order to obtain a highly sensitive cr (vi) detection technique, researchers have conducted a series of studies. In 2011, Sereshti et al detected Cr (VI) at a concentration of 0.0044. mu. mol/L using ICP-OES. In 2015, Ravishankar et al electrochemically detected Cr (VI) at a concentration of 0.033. mu. mol/L. In 2016, Vidal et al detected Cr (VI) at a concentration of 0.058. mu. mol/L using atomic absorption spectroscopy. Compared with the detection technology of Cr (VI), the SERS optical fiber sensor not only can realize simple, quick and high-sensitivity Cr (VI) detection, but also has the detection advantages of flexibility, real-time performance, in-situ performance, long distance and low loss, so that the Cr (VI) detection technology is greatly optimized, and no technical disclosure about optical fiber probes or SERS optical fiber sensors for detecting Cr (VI) exists at present.
Disclosure of Invention
One of the purposes of the invention is to provide a silver-plated optical fiber Raman probe, which adopts methimazole functionalization to realize ultrahigh sensitivity and oxidation resistance of detection of an object to be detected, and provides a new idea and method for detection of pollutants in water.
The invention also aims to provide a preparation method of the silver-plated optical fiber Raman probe, which has the advantages of simple preparation process, good repeatability, good stability and good anti-interference performance.
The invention also aims to provide application of the silver-plated optical fiber Raman probe.
The scheme adopted by the invention for realizing one of the purposes is as follows: a silver-plated optical fiber Raman probe realizes Cr (VI) detection by adopting methimazole as a Raman signal molecule.
Preferably, the silver-plated optical fiber raman probe comprises an optical fiber body, a silver plating layer coated on the surface of the optical fiber body, and a methimazole functional layer adsorbed on the surface of the silver plating layer.
The second scheme adopted by the invention for achieving the purpose is as follows: the preparation method of the silver-plated optical fiber Raman probe adopts a stannous chloride sensitized auxiliary solvent thermal method and combines methimazole functionalization to prepare the silver-plated optical fiber Raman probe.
Preferably, the method comprises the following steps:
(1) optical fiber sensitization pretreatment: soaking the optical fiber to be treated in a stannous chloride aqueous solution for sensitization treatment;
(2) preparing a precursor solution: preparing a soluble silver salt solution and a sodium bicarbonate solution, adding a surfactant into the uniformly stirred soluble silver salt solution, and pouring and uniformly mixing the sodium bicarbonate solution after the surfactant is dissolved;
(3) preparing a silver-plated optical fiber by a solvothermal method: putting the optical fiber into the prepared precursor solution, sealing, and reacting at a certain temperature to be complete to obtain the silver-plated optical fiber;
(4) methimazole functionalization: soaking the prepared silver-plated optical fiber in methimazole birutan-robinson (BR) buffer solution with a certain concentration added with halide salt, taking out after functionalization is completed, washing to remove residues, and drying in an inert atmosphere to obtain the silver-plated optical fiber Raman probe.
Preferably, in the step (1), the concentration of the stannous chloride aqueous solution is 0-2 wt%.
Preferably, in the step (2), the soluble silver salt is silver nitrate; the surfactant is polyvinylpyrrolidone, polyethylene glycol or hexadecyl ammonium bromide; wherein the molar ratio of the surfactant to the soluble silver salt is 0-16: 1, the molar ratio of the soluble silver salt to the sodium bicarbonate is 1-2: 1, the concentration of the soluble silver salt is 0.01-1 mol/L.
Preferably, in the step (3), the reaction temperature is 120-220 ℃.
Preferably, in the step (4), the methimazole concentration is 10-70.1mol/L, the functionalization time is 10min to 2h, the concentration of the halide salt is 0 to 1mol/L, and the pH value of the BR buffer solution is 2 to 7.
Preferably, in the step (4), the halide salt is at least one of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide and potassium iodide.
The scheme adopted by the invention for realizing the third purpose is as follows: the application of the silver-plated optical fiber Raman probe is to apply the silver-plated optical fiber Raman probe to an SERS optical fiber Raman sensor.
The invention has the following advantages and beneficial effects:
the silver-plated optical fiber Raman probe provided by the invention realizes Cr (VI) ultrasensitive detection and excellent oxidation resistance by adopting methimazole functionalization.
The preparation method provided by the invention has the advantages of simple process, high sensitivity, good repeatability, good stability and good anti-interference performance, and realizes the shape regulation of the silver nanoparticles on the end face of the optical fiber and the strong interface adhesion of the optical fiber and the silver nano material by adopting a stannous chloride-assisted solvothermal method. Specifically, the stannous chloride pretreatment process promotes the silver nanoparticles on the end face of the optical fiber to grow compactly and uniformly on the one hand, and enhances the interface adhesion between the optical fiber and the silver nanoparticles on the other hand. By adopting methimazole functionalization, Cr (VI) ultrasensitive detection and excellent oxidation resistance are realized.
The SERS optical fiber sensor prepared by the silver-plated optical fiber Raman probe can realize flexible, real-time, in-situ, remote and low-loss detection, and can be applied to detection in the fields of environment and the like. Compared with the traditional Cr (VI) detection technology, the SERS optical fiber sensor disclosed by the invention is used for nondestructive and rapid detection, complex sample pretreatment and redundant detection reagents are not needed, the simple, rapid and ultrahigh-sensitivity detection is realized, the detection technology suitable for Cr (VI) is widened, and the detection convenience and sensitivity are greatly optimized. The SERS optical fiber sensor has ultrahigh sensitivity and can detect the concentration of 10-11Cr (VI) with mol/L and above, excellent oxidation resistance, repeatability and interference resistance, and is suitable for the field of environmental detection.
Drawings
FIG. 1 is a schematic diagram of a SERS fiber sensor of the present invention;
FIG. 2 shows SERS optical fiber sensor detection 10 in embodiment 1 of the present invention-5mol/L-10-11Surface Enhanced Raman Scattering (SERS) of mol/L Cr (VI) solution;
FIG. 3 is a diagram showing the UV-VIS absorption spectrum of a silver-coated optical fiber probe reaction solution in example 2 of the present invention;
FIG. 4 is an SEM image of a silver-coated optical fiber probe of example 3 of the present invention at a scale of 5 μm;
FIG. 5 shows the oxidation resistance of the SERS optical fiber sensor in example 4 of the present invention;
FIG. 6 is a diagram showing the repeatability of the SERS optical fiber sensor in example 5 of the present invention;
FIG. 7 is the interference immunity of the SERS optical fiber sensor in example 6 of the present invention;
in the figure: the device comprises a silver-plated optical fiber probe (1), a laser (2), a first signal transmission device (3), a microscope objective (4), a filtering and second signal transmission device (5), a signal collecting device (6) and a computer (7).
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1:
a silver-plated optical fiber Raman probe is prepared by the following steps:
1) optical fiber sensitization pretreatment: and (3) soaking the quartz optical fiber with a smooth end face and clean and dry in a stannous chloride aqueous solution with the mass fraction of 0.2 wt% for 3min for sensitization treatment.
2) Preparing a precursor solution: preparing 30mL of silver nitrate solution with the concentration of 0.067mol/L and 30mL of sodium bicarbonate solution with the concentration of 0.04mol/L, adding 1.776g of polyvinylpyrrolidone after the silver nitrate is completely dissolved, stirring uniformly, adding the sodium bicarbonate solution which is completely dissolved, and continuing to stir uniformly.
3) Preparing a silver-plated optical fiber by a solvothermal method: and pouring the prepared precursor solution into a polytetrafluoroethylene high-pressure kettle, putting an optical fiber into the high-pressure kettle, sealing the container, and reacting for 1h at 140 ℃. And after the reaction is finished and naturally cooled, taking out the optical fiber.
4) Methimazole functionalization: and soaking the prepared silver-plated optical fiber in 0.1mol/L methimazole BR (Burkitan-Robinson) buffer solution (pH 3) added with 0.075mol/L sodium chloride for 40min, taking out after functionalization is completed, washing residual solution with distilled water, drying under argon to obtain a silver-plated optical fiber Raman probe, and storing.
The silver-plated optical fiber Raman probe prepared in the embodiment 1 is used for preparing a SERS optical fiber sensor, as shown in fig. 1, the SERS optical fiber sensor specifically comprises: the device comprises a silver-plated optical fiber probe (1), a laser (2), a first signal transmission device (3), a microscope objective (4), a filtering and second signal transmission device (5), a signal collecting device (6) and a computer (7). Laser emitted by the laser (2) reaches the microscope objective (4) through the first signal transmission device (3) and then is emitted to the near end face of the silver-plated optical fiber probe (1). Incident laser reaches the distal end face that carries silver nanoparticle through optic fibre after, with the material interact who adsorbs on silver nanoparticle surface, the SERS signal of collecting transmits back microscope objective (4) through same root optical fiber, through filtering and second signal transmission device (5), reachs signal collection device (6) to demonstrate the SERS spectrum that detects through computer (7).
Respectively soaking SERS optical fiber sensors in the solution with the concentration of 10-5mol/L、10-6mol/L、10-7mol/L、10-8mol/L、10-9mol/L、10-10mol/L and 10-11Soaking in mol/L Cr (VI) solution for 30min, taking out, and testing the SERS spectrum of the sensor before and after soaking.
FIG. 2 shows the SERS optical fiber sensor test 10 of this embodiment 1-5mol/L-10-11The surface enhanced Raman scattering spectra of the mol/L Cr (VI) solution are all 1363cm-1A strong absorption peak is formed, which shows that the SERS optical fiber sensor has excellent surface enhanced Raman scattering performance.
Example 2:
a silver-plated optical fiber Raman probe is prepared by the following steps:
1) optical fiber sensitization pretreatment: and (3) soaking the quartz optical fiber with a smooth end face and clean and dry in a stannous chloride aqueous solution with the mass fraction of 0.1 wt% for 1min for sensitization treatment.
2) Preparing a precursor solution: preparing 30mL of silver nitrate solution with the concentration of 0.01mol/L and 30mL of sodium bicarbonate solution with the concentration of 0.01mol/L, adding 3.552g of polyvinylpyrrolidone after the silver nitrate is completely dissolved, stirring uniformly, adding the sodium bicarbonate solution completely dissolved, and continuing to stir uniformly.
3) Preparing a silver-plated optical fiber by a solvothermal method: and pouring the prepared precursor solution into a polytetrafluoroethylene high-pressure kettle, putting an optical fiber into the high-pressure kettle, sealing the container, and reacting for 24 hours at 120 ℃. And after the reaction is finished and naturally cooled, taking out the optical fiber.
4) Methimazole functionalization: soaking the prepared silver-plated optical fiber in 10 parts with 0mol/L sodium bromide-7Soaking in mol/L methimazole BR (Bertany-Robinson) buffer solution (pH 2) for 10min, taking out after functionalization is completed, washing residual solution with distilled water, drying under argon to obtain the silver-plated optical fiber Raman probe, and storing.
The silver-plated fiber raman probe prepared in example 2 was used to prepare the same SERS fiber sensor as in example 1. And soaking the obtained SERS optical fiber sensor in a Cr (VI) solution to be tested for 10min, taking out, and testing the SERS spectrum of the sensor before and after soaking.
The SERS optical fiber sensor obtained in example 2 has a layer of material with metallic luster loaded on the end face and the side face, and the concentration of the material can be detected to be 10-6A Cr (VI) solution in a molar ratio of at least one.
FIG. 3 is a diagram of the UV-VIS absorption spectrum of the silver-coated optical fiber reaction solution in example 2 of the present invention, from which the resonance peak of the sample obtained at 420nm is shown, indicating the presence of silver nanoparticles in the sample.
Example 3:
a silver-plated optical fiber Raman probe and a preparation method thereof comprise the following steps:
1) optical fiber sensitization pretreatment: and soaking the quartz optical fiber with the conical end face and cleaned and dried in a stannous chloride aqueous solution with the mass fraction of 2 wt% for 2min for sensitization treatment.
2) Preparing a precursor solution: preparing 30mL of silver nitrate solution with the concentration of 0.5mol/L and 30mL of sodium bicarbonate solution with the concentration of 1mol/L, adding 0g of polyvinylpyrrolidone after the silver nitrate is completely dissolved, stirring uniformly, adding the sodium bicarbonate solution completely dissolved, and continuing stirring until the mixture is uniform.
3) Preparing a silver-plated optical fiber by a solvothermal method: and pouring the prepared precursor solution into a polytetrafluoroethylene high-pressure kettle, putting an optical fiber into the high-pressure kettle, sealing the container, and reacting for 8 hours at 160 ℃. And after the reaction is finished and naturally cooled, taking out the optical fiber.
4) Methimazole functionalization: soaking the prepared silver-plated optical fiber in 10 parts with 0.15mol/L sodium iodide- 6Soaking in mol/L methimazole BR (Bertany-Robinson) buffer solution (pH 4) for 20min, taking out after functionalization is completed, washing residual solution with distilled water, drying under argon to obtain the silver-plated optical fiber Raman probe, and storing.
The silver-plated fiber raman probe prepared in example 3 was used to prepare the same SERS fiber sensor as in example 1. And soaking the obtained SERS optical fiber sensor in a Cr (VI) solution to be tested for 20min, taking out, and testing the SERS spectrum of the sensor before and after soaking.
The SERS optical fiber sensor obtained in example 3 has a layer of material with metallic luster loaded on the end face and the side face, and the concentration of the material can be detected to be 10-7A Cr (VI) solution in a molar ratio of at least one.
FIG. 4 is an SEM image of the end surface of a silver-plated optical fiber probe of example 3 of the present invention on a scale of 5 μm. As can be seen, the end face of the optical fiber was grown with spherical silver nanoparticles having an average grain size of 75 nm.
Example 4:
a silver-plated optical fiber Raman probe is prepared by the following steps:
1) optical fiber sensitization pretreatment: and (3) soaking the clean and dry sapphire optical fiber with a flat end face in a stannous chloride aqueous solution with the mass fraction of 0 wt% for 4min for sensitization treatment.
2) Preparing a precursor solution: preparing 30mL of silver nitrate solution with the concentration of 0.05mol/L and 30mL of sodium bicarbonate solution with the concentration of 0.05mol/L, adding 2g of polyvinylpyrrolidone after the silver nitrate is completely dissolved, stirring uniformly, adding the sodium bicarbonate solution completely dissolved, and continuing to stir uniformly.
3) Preparing a silver-plated optical fiber by a solvothermal method: and pouring the prepared precursor solution into a polytetrafluoroethylene high-pressure kettle, putting an optical fiber into the high-pressure kettle, sealing the container, and reacting for 1h at 220 ℃. And after the reaction is finished and naturally cooled, taking out the optical fiber.
4) Methimazole functionalization: soaking the prepared silver-plated optical fiber in 10 parts with 1mol/L potassium bromide-3Soaking in mol/L methimazole BR (Bertany-Robinson) buffer solution (pH 5) for 30min, taking out after functionalization is completed, washing residual solution with distilled water, drying under argon to obtain the silver-plated optical fiber Raman probe, and storing.
The silver-plated fiber raman probe prepared in example 4 was used to prepare the same SERS fiber sensor as in example. And soaking the obtained SERS optical fiber sensor in a Cr (VI) solution to be tested for 60min, taking out, and testing the SERS spectrum of the sensor before and after soaking.
The SERS optical fiber sensor obtained in example 4 has a layer of material with metallic luster loaded on the end face and the side face, and the concentration of the material can be detected to be 10-6A Cr (VI) solution in a molar ratio of at least one.
FIG. 5 shows SERS spectra of SERS fiber sensor in example 4 of the present invention after being placed in air for 0 day and 14 days. The change of the peak intensity of the SERS spectrum is 36%, and good stability is shown.
Example 5:
a silver-plated optical fiber Raman probe is prepared by the following steps:
1) optical fiber sensitization pretreatment: and (3) soaking the clean and dry photonic crystal fiber with a smooth end face in a stannous chloride aqueous solution with the mass fraction of 1 wt% for 30min for sensitization treatment.
2) Preparing a precursor solution: preparing 30mL of silver nitrate solution with the concentration of 1mol/L and 30mL of sodium bicarbonate solution with the concentration of 1.5mol/L, adding 0.132g of polyethylene glycol after the silver nitrate is completely dissolved, stirring uniformly, adding the sodium bicarbonate solution completely dissolved, and continuing to stir uniformly.
3) Preparing a silver-plated optical fiber by a solvothermal method: and pouring the prepared precursor solution into a polytetrafluoroethylene high-pressure kettle, putting an optical fiber into the high-pressure kettle, sealing the container, and reacting for 12 hours at 180 ℃. And after the reaction is finished and naturally cooled, taking out the optical fiber.
4) Methimazole workEnergy conversion: soaking the prepared silver-plated optical fiber in 10 parts with 1mol/L potassium chloride-3Soaking in mol/L methimazole BR (Bertany-Robinson) buffer solution (pH 5) for 30min, taking out after functionalization is completed, washing residual solution with distilled water, drying under argon to obtain the silver-plated optical fiber Raman probe, and storing.
The silver-plated fiber raman probe prepared in example 5 was used to prepare the same SERS fiber sensor as in example. And soaking the obtained SERS optical fiber sensor in a Cr (VI) solution to be tested for 60min, taking out, and testing the SERS spectrum of the sensor before and after soaking.
The SERS optical fiber sensor obtained in example 5 has a layer of material with metallic luster loaded on the end face and the side face, and the concentration of the material can be detected to be 10-8A Cr (VI) solution in a molar ratio of at least one.
FIG. 6 is a repeatability test of SERS fiber sensor in example 5 of the present invention. The SERS spectra detected by 6 optical fiber sensors have similar peak shapes and similar intensities, and show excellent repeatability.
Example 6:
a silver-plated optical fiber Raman probe is prepared by the following steps:
1) optical fiber sensitization pretreatment: and (3) soaking the quartz optical fiber with a smooth end face and clean and dry in a stannous chloride aqueous solution with the mass fraction of 1.2 wt% for 15min for sensitization treatment.
2) Preparing a precursor solution: preparing 30mL of silver nitrate solution with the concentration of 0.2mol/L and 30mL of sodium bicarbonate solution with the concentration of 0.3mol/L, adding 1.2g of hexadecyl ammonium bromide after the silver nitrate is completely dissolved, stirring uniformly, adding the sodium bicarbonate solution completely dissolved, and continuing to stir uniformly.
3) Preparing a silver-plated optical fiber by a solvothermal method: and pouring the prepared precursor solution into a polytetrafluoroethylene high-pressure kettle, putting an optical fiber into the high-pressure kettle, sealing the container, and reacting for 4 hours at 200 ℃. And after the reaction is finished and naturally cooled, taking out the optical fiber.
4) Methimazole functionalization: and soaking the prepared silver-plated optical fiber in 0.1mol/L methimazole BR (Burkitan-Robinson) buffer solution (pH 7) added with 0.075mol/L sodium iodide to obtain a silver-plated optical fiber Raman probe, and storing.
The silver-plated fiber raman probe prepared in example 6 was used to prepare the same SERS fiber sensor as in example. And soaking the obtained SERS optical fiber sensor in a Cr (VI) solution to be tested for 30min, taking out, and testing the SERS spectrum of the sensor before and after soaking.
The SERS optical fiber sensor obtained in example 6 has a layer of material with metallic luster loaded on the end face and the side face, and the concentration of the material can be detected to be 10-7A Cr (VI) solution in a molar ratio of at least one.
Fig. 7 is an anti-interference test of the SERS optical fiber sensor in embodiment 6 of the present invention. When other interfering ions with the Cr (VI) concentration of 100 times are added, the SERS spectral intensity is almost unchanged, and good interference resistance is shown.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A silver-plated optical fiber Raman probe is characterized in that: and (3) detecting Cr (VI) by using methimazole as a Raman signal molecule.
2. The silver-plated fiber raman probe according to claim 1, wherein: the silver-plated optical fiber Raman probe comprises an optical fiber body, a silver plating layer coated on the surface of the optical fiber body and a methimazole functional layer adsorbed on the surface of the silver plating layer.
3. A method for preparing a silver-plated fiber raman probe according to claim 1 or 2, characterized in that: a stannous chloride sensitized auxiliary solvent thermal method is adopted, and methimazole functionalization is combined to prepare the silver-plated optical fiber probe.
4. The method for preparing the silver-plated fiber Raman probe according to claim 3, comprising the steps of:
(1) optical fiber sensitization pretreatment: soaking the optical fiber to be treated in a stannous chloride aqueous solution for sensitization treatment;
(2) preparing a precursor solution: preparing a soluble silver salt solution and a sodium bicarbonate solution, adding a surfactant into the uniformly stirred soluble silver salt solution, and pouring and uniformly mixing the sodium bicarbonate solution after the surfactant is dissolved;
(3) preparing a silver-plated optical fiber by a solvothermal method: putting the optical fiber into the prepared precursor solution, sealing, and reacting at a certain temperature to be complete to obtain the silver-plated optical fiber;
(4) methimazole functionalization: soaking the prepared silver-plated optical fiber in methimazole birutan-robinson (BR) buffer solution with a certain concentration added with halide salt, taking out after functionalization is completed, washing to remove residues, and drying in an inert atmosphere to obtain the silver-plated optical fiber Raman probe.
5. The method for preparing a silver-plated fiber Raman probe according to claim 4, wherein the method comprises the following steps: in the step (1), the concentration of the stannous chloride aqueous solution is 0-2 wt%.
6. The method for preparing a silver-plated fiber Raman probe according to claim 4, wherein the method comprises the following steps: in the step (2), the soluble silver salt is silver nitrate; the surfactant is polyvinylpyrrolidone, polyethylene glycol or hexadecyl ammonium bromide; wherein the molar ratio of the surfactant to the soluble silver salt is 0-16: 1, the molar ratio of the soluble silver salt to the sodium bicarbonate is 1-2: 1, the concentration of the soluble silver salt is 0.01-1 mol/L.
7. The method for preparing a silver-plated fiber Raman probe according to claim 4, wherein the method comprises the following steps: in the step (3), the reaction temperature is 120-220 ℃.
8. The method for preparing a silver-plated fiber Raman probe according to claim 4, wherein the method comprises the following steps: in the step (4), the concentration of the methimazole is 10-70.1mol/L, the functionalization time is 10min to 2h, the concentration of the halide salt is 0 to 1mol/L, and the pH value of the BR buffer solution is 2 to 7.
9. The method for preparing a silver-plated fiber Raman probe according to claim 4, wherein the method comprises the following steps: in the step (4), the halide salt is at least one of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide and potassium iodide.
10. The application of the silver-plated optical fiber Raman probe is characterized in that: the silver-plated fiber Raman probe according to claim 1 or 2 or the silver-plated fiber Raman probe prepared by the preparation method according to any one of claims 3 to 9 is applied to a SERS fiber Raman sensor.
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