CN112710647B - Optical fiber Raman probe for water pollution detection - Google Patents
Optical fiber Raman probe for water pollution detection Download PDFInfo
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- CN112710647B CN112710647B CN202011411630.XA CN202011411630A CN112710647B CN 112710647 B CN112710647 B CN 112710647B CN 202011411630 A CN202011411630 A CN 202011411630A CN 112710647 B CN112710647 B CN 112710647B
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- optical fiber
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
Abstract
The invention relates to an optical fiber Raman probe for water pollution detection, which mainly comprises an excitation optical fiber, a collection optical fiber, a focusing lens and a Raman enhanced substrate reflecting mirror. The excitation light excites the optical fiber through the probe, the aqueous solution on the reflection mirror of the Raman enhancement substrate is excited, and the excited Raman information is collected by the collecting optical fiber and sent to a Raman spectrometer for analysis. And a focusing lens is designed at the front end of the probe to improve excitation and collection efficiency, an optical filter set is increased, and the signal-to-noise ratio of Raman spectrum signals is reduced. The probe is mainly designed by a Raman enhanced substrate reflecting mirror, so that the Raman spectrum of a material index in water pollution is greatly improved, and qualitative and quantitative analysis of the Raman spectrum is realized.
Description
Technical Field
The invention relates to an optical fiber Raman probe, in particular to an optical fiber Raman probe for water pollution detection.
Background
With the development of modern industry and society, high-quality water resources on which human beings live are becoming more and more rare and precious, which is mainly a result of the increasingly serious water pollution problem and the increasingly threatening normal utilization of water resources. Therefore, the prevention and treatment of water pollution has become a big thing to improve and save the living environment of human beings, and is a real problem which is closely related to our daily life and directly affects our quality of life and physical health. The source of water pollution is mainly related to the following aspects:
(1) Industrial emission pollution: including industries such as chemical industry, pharmacy, coking, petrifaction, printing and dyeing, papermaking, and emerging cosmetic manufacturing, and the organic components in the wastewater comprise benzene, phenol and chlorobenzene pollutants.
(2) Pollution of drinking water: in the project, we mainly consider pollution sources in drinking water, which may threaten human health or physical functions, and focus on organic pollutants which are difficult to detect conventionally, such as carcinogenic, teratogenic and endocrine disruptors and the like, involved in the current water pollution control process.
(3) Domestic sewage discharge: mainly refers to the sewage such as daily chemical pollution, excrement and urine.
(4) Medical pollution discharge: the sewage discharged from medical units may carry contaminants such as medicines, infectious viruses, etc.
(5) Agricultural pollution discharge: mainly consider the possible pollutants of chemical fertilizers, pesticides, feces and the like.
(6) Natural pollution: the evolution of the natural environment, natural precipitation, river, atmospheric flow, etc. can also lead to the movement and formation of pollution. The water pollutants mainly comprise organic compounds such as carbohydrates, phosphorus, nitrogen, chloride, sulfides, oils and proteins and the like.
Indeed, the emission standards vary from industry to industry, considering the different pollutants. After being discharged, the industrial sewage is mixed with domestic sewage and enters a sewage treatment plant for treatment, and the components and the content are extremely complex. The method for treating the organic pollutants by the sewage treatment plant mainly aims at adding a strong oxidant to the total content of the organic matters. At present, the discharge index of the sewage treatment plant only examines whether the total discharge amount of the organic pollutants reaches the standard or not, and the discharge content of the specific pollutants is not detected. Although the total amount of organic pollutants in the treated sewage reaches the emission standard, persistent organic pollutants may not be effectively decomposed and even be emitted in the content close to the original content. Therefore, small or trace amounts of pollutants with large toxicity and difficult degradation are discharged to the natural environment, and after the pollutants are continuously accumulated, the content of the pollutants in the natural environment of a certain area is increased. This places higher and more stringent demands on real-time, continuous monitoring of environmental pollution.
The preferred biodegradation method for sewage treatment is to decompose and degrade macromolecular pollutants containing elements such as carbohydrate, protein, amino acid, nitrogen, sulfur and the like into biodegradable micromolecular components containing the same elements, and hopefully produce resources or energy products such as hydrogen, methane and the like which can be reused, or harmless substances such as water, nitrogen and the like, and avoid producing greenhouse gases such as carbon dioxide and the like, or harmful substances such as benzene, aldehydes, chlorine and sulfur and the like.
Timely and accurate detection and monitoring of water pollution is a primary and key link of water pollution control and treatment. Currently, the existing detection technologies mainly comprise widely applied industrialized technologies such as COD (chemical oxygen demand), BOD (biochemical oxygen demand) and the like, biological item detection technologies aiming at biological cells and infectious agents, and conventional detection technologies such as chromatography, mass spectrometry and the like after chemical separation in a laboratory (aiming at phenols, trichloro, pentachloro compounds, carcinogens and the like in sewage). The detection technology involves expensive instruments, complex operation, complicated detection steps and long period, and in particular in trace detection, multistage detection is often required, and sometimes gas phase/liquid phase chromatography and mass spectrum are combined, so that on-site and real-time monitoring is difficult to realize. In addition, some compounds can only be qualitatively detected but cannot be detected, and particularly for sewage samples, the method capable of being used in drinking water cannot be used due to large background noise, large interference and the like in sewage.
Raman spectroscopy has the ability to provide specific information on a variety of chemical and morphological components that are not available by other methods, and thus raman spectroscopic species detection capabilities have been determined. The design of fiber optic probes has advanced significantly over the past decade, indicating that raman spectroscopy is a potential, useful clinical technique. Currently, there are commercially available probes, but most of them are limited to high concentration solution detection because the excitation wavelength and optical structure used are not optimized for use in water pollution detection.
The Raman spectrum is a scattering spectrum, the Raman effect is weak, and because of the real-time detection requirement, the time for the excitation light to enter the aqueous solution is relatively short, and the obtained Raman spectrum effect is weak. There is therefore a need to employ surface enhanced raman techniques (SERS) to increase the signal-to-noise ratio of raman spectra. The characteristic contaminant molecules are identified by utilizing the contrast characterization of various parameters such as characteristic fluorescence emission spectrum, characteristic absorption peak, characteristic spectrum corresponding to chemical bond or functional group and the like of the contaminant fingerprint molecules, but the surface enhancement technology is not applied to probe manufacture in the current optical fiber probe, so that the collection efficiency of the probe is low.
It is therefore necessary to design a fiber raman probe for low concentration detection of water contamination that incorporates surface enhanced raman techniques.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an optical fiber Raman probe for detecting water pollution, which increases the applicability of the device.
In order to solve the technical problems, the invention adopts the following technical scheme: the optical fiber Raman probe for water pollution detection comprises a probe protective sleeve, wherein a Raman enhanced substrate reflecting mirror, a spherical focusing lens and an optical fiber bundle are arranged in the probe protective sleeve from top to bottom; the Raman enhanced substrate reflector comprises a cylindrical lens and an inclined reflector, and gold nanoparticles are uniformly arranged on the surface of the inclined reflector; the optical fiber group comprises a collecting optical fiber and an excitation optical fiber, wherein the collecting optical fiber is uniformly wrapped on the outer wall of the excitation optical fiber, and an optical fiber bundle protecting sleeve is wrapped on the outer wall of the collecting optical fiber.
Preferably, the excitation optical fiber is a multimode pure quartz optical fiber, and the core diameter is 50/62.6/100um; the collecting optical fiber is a multimode pure quartz optical fiber, and the core diameter is 50/62.6/100um.
Preferably, the collection optical fibers are arranged in six, and the six collection optical fibers are uniformly distributed around the excitation optical fiber.
Preferably, the inclined mirror is inclined at 45 ° to the probe end face.
Preferably, the probe protective sleeve material is aluminum sheet.
Preferably, the fiber bundle protective sleeve material is a polymer.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention combines the surface enhancement technology with the optical fiber Raman technology, improves the signal-to-noise ratio of Raman spectrum, and more effectively detects low-concentration water pollution;
2. the Raman probe with the surface enhancement effect has the characteristics of simple structure, convenient operation, high sensitivity and high reliability, and overcomes the defects that the conventional Raman probe has weaker Raman effect, lower signal-to-noise ratio and can not extract effective information with high sensitivity and high precision.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed.
Drawings
Further objects, functions and advantages of the present invention will be clarified by the following description of embodiments of the present invention with reference to the accompanying drawings, in which:
fig. 1 schematically shows a schematic diagram of a fiber-optic raman probe according to the invention.
In the figure:
1. cylindrical lens 2 and oblique mirror
3. Spherical focusing lens 4 and probe protective sleeve
5. Collecting optical fiber 6, excitation optical fiber
7. Optical fiber bundle protective sleeve
Detailed Description
The objects and functions of the present invention and methods for achieving these objects and functions will be elucidated by referring to exemplary embodiments. However, the present invention is not limited to the exemplary embodiments disclosed below; this may be implemented in different forms. The essence of the description is merely to aid one skilled in the relevant art in comprehensively understanding the specific details of the invention.
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the drawings, the same reference numerals represent the same or similar components, or the same or similar steps.
Aiming at the defects in the prior art, the invention aims to provide a Raman spectrum measurement probe capable of entering liquid to detect low-concentration water pollution in real time. The surface enhancement technology is combined with the optical fiber Raman technology, so that the signal-to-noise ratio of the Raman spectrum is improved, and the low-concentration water pollution is detected more efficiently. The Raman probe with the surface enhancement effect has the characteristics of simple structure, convenient operation, high sensitivity and high reliability, and overcomes the defects that the conventional Raman probe has weaker Raman effect, lower signal-to-noise ratio and cannot extract effective information with high sensitivity and high precision.
In order to achieve the purpose, the design target of the Raman probe is that a Raman enhancement substrate reflecting mirror is designed at the front end of the probe, the reflecting mirror is arranged at an angle of 45 degrees, gold nano particles are uniformly distributed on the reflecting mirror, the surface enhancement effect of Raman spectrum is ensured, and the Raman spectrum signal is greatly improved; the optical fiber probe excitation light and the collection light focus are ensured to be positioned on the surface of the reflecting mirror, and Raman spectrum information of low-concentration substances in water pollution is excited and collected to the greatest extent, so that the optical fiber probe excitation light and collection light focus are used for qualitative and quantitative analysis.
The invention consists of the following parts, as shown in figure 1: the surface of the inclined reflector 2, the spherical focusing lens 3, the probe protecting sleeve 4, the collecting optical fiber 5, the exciting optical fiber 6 and the optical fiber bundle protecting sleeve 7.
The main principle and the using method of the probe are as follows: the Raman enhanced substrate radiation mirror is used in the probe structure, the key structure is that the surface of the inclined reflecting mirror 2 with gold nanoparticles is provided with a Raman spectrum surface enhancement effect, and the signal-to-noise ratio of the Raman spectrum is greatly improved. In the use process, the laser emits laser through the excitation optical fiber 6, the laser is concentrated on the surface 2 of the reflector with gold nanoparticles through the spherical focusing lens 3, the surface of the inclined reflector 2 with gold nanoparticles is contacted with liquid with pollutants, the local electromagnetic field enhancement caused by surface plasmon resonance (Surface plasmon resonance, SPR) is generated through the surface enhanced Raman effect, the Raman spectrum signal of the pollutants in the tested liquid is increased, the laser is reflected by the Raman enhanced substrate reflector, and enters the collecting optical fiber 5 through the spherical focusing lens 3, the collecting optical fiber 5 is composed of 6 optical fibers, and the collecting optical fibers are uniformly distributed around the excitation optical fiber.
In the optical fiber Raman probe structure, a Raman enhancement substrate reflecting mirror consists of a cylindrical lens 1 and an inclined reflecting mirror 2, the inclined angle of the inclined reflecting mirror 2 relative to the end face of a probe is 45 degrees, a certain number of gold nanoparticles are uniformly designed on the surface of the inclined reflecting mirror 2 with the gold nanoparticles, and the reflection efficiency of the reflecting mirror surface and the Raman signal enhancement effect are ensured.
In the invention, the spherical focusing lens 3 is used for focusing excitation light and collecting light, and focusing the focus on the surface of the inclined reflecting mirror 2 with gold nanoparticles, so that the signal-to-noise ratio of a Raman spectrum is improved, and the excitation efficiency of the excitation light and the collection efficiency of the collection optical fiber are improved.
The probe protective sleeve 4 is made of aluminum sheets, so that no Raman spectrum is generated, and meanwhile, the probe protective sleeve is used for connecting the Raman enhancement substrate reflecting mirror and the optical fiber group protective sleeve 7, and the Raman enhancement substrate reflecting mirror and the optical fiber group protective sleeve 7 are integrated through gluing and welding, so that the strength of the optical fiber probe is improved.
The optical fiber Raman probe collecting optical fiber 5 selects multimode pure quartz optical fibers, reduces the generation of optical fiber Raman spectrum, has the fiber core diameter of 50/62.6/100um, designs a series of collecting optical fibers, selects an application requirement and an equipped Raman spectrometer as a reference, designs the collecting optical fibers into optical fiber bundles arranged in a single row, adapts to the slit shape of the equipped Raman spectrometer, and improves the Raman light collecting efficiency.
The excitation optical fiber 6 in the invention adopts multimode pure quartz optical fiber, reduces the generation of fiber Raman spectrum, has the core diameter of 50/62.6/100um, and designs a series of excitation optical fibers to meet different application requirements.
The optical fiber bundle protective sleeve 7 is made of polymer materials and is used for fixing the probe optical fiber bundle and connecting the probe protective sleeve 4, and the flexibility of the probe can be improved by adopting the polymer, so that the optical fiber bundle protective sleeve is suitable for Raman spectrum detection of different application scenes.
The beneficial effects of the invention are as follows: the invention combines the surface enhancement technology with the optical fiber Raman technology, improves the signal-to-noise ratio of Raman spectrum, and more effectively detects low-concentration water pollution; the Raman probe with the surface enhancement effect has the characteristics of simple structure, convenient operation, high sensitivity and high reliability, and overcomes the defects that the conventional Raman probe has weaker Raman effect, lower signal-to-noise ratio and can not extract effective information with high sensitivity and high precision.
Other embodiments of the invention will be apparent to and understood by those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
Claims (4)
1. A fiber optic raman probe for water pollution detection comprising: the probe protective sleeve is internally provided with a Raman enhanced substrate reflecting mirror, a spherical focusing lens and an optical fiber bundle from top to bottom;
the Raman enhanced substrate reflector comprises a cylindrical lens and an inclined reflector, and gold nanoparticles are uniformly arranged on the surface of the inclined reflector; the surface of the inclined reflecting mirror with gold nano particles is contacted with the liquid with pollutants, surface plasmon resonance is generated through the surface enhanced Raman effect, and the local electromagnetic field is enhanced, so that the Raman spectrum signal of the pollutants in the liquid to be detected is increased;
the optical fiber bundle comprises a collecting optical fiber and an excitation optical fiber, wherein the collecting optical fiber is uniformly wrapped on the outer wall of the excitation optical fiber, and an optical fiber bundle protective sleeve is wrapped on the outer wall of the collecting optical fiber;
the inclined reflecting mirror is inclined by 45 degrees relative to the end face of the probe;
the collecting optical fiber is a multimode pure quartz optical fiber; the probe protective sleeve is made of aluminum sheet.
2. The fiber optic raman probe according to claim 1 wherein said excitation fiber is a multimode pure quartz fiber having a core diameter of 50/62.6/100um; the core diameter of the collecting optical fiber is 50/62.6/100um.
3. A fiber-optic raman probe according to claim 2, wherein said collection fibers are provided with six, six of said collection fibers being evenly arranged around said excitation fiber.
4. The fiber optic raman probe according to claim 1 wherein said fiber bundle protective sheath material is a polymer.
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| CN113189082B (en) * | 2021-05-07 | 2022-11-08 | 中国科学院地理科学与资源研究所 | Trace organic pollutant analytical spectrometer based on double-pulse-width laser and detection method |
| CN113075214B (en) * | 2021-05-07 | 2023-06-16 | 北京中仪智控科技有限公司 | Detection probe and detection analysis method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1815197A (en) * | 2006-02-24 | 2006-08-09 | 清华大学 | Photon crystal optical-fiber probe sensor based on nano grain surface increasing Raman spectrum |
| WO2015085978A1 (en) * | 2013-12-09 | 2015-06-18 | Friedrich-Schiller-Universität Jena | Device with a raman probe, and method using said device |
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| WO2010144081A1 (en) * | 2009-06-10 | 2010-12-16 | University Of Utah Research Foundation | Apparatus for raman spectroscopy having an optical fiber probe |
| CN205538685U (en) * | 2016-03-15 | 2016-08-31 | 安徽芯核防务装备技术股份有限公司 | Integral type binary channels raman spectroscopy collection probe |
| CN107478640A (en) * | 2017-08-04 | 2017-12-15 | 中国科学院合肥物质科学研究院 | A kind of enhanced Portable Raman spectrometer of optical fiber probe |
| CN109730694A (en) * | 2019-01-08 | 2019-05-10 | 北京信息科技大学 | The raman spectroscopy measurement probe of plaque type in a kind of diagnosis human vas |
| CN109730640A (en) * | 2019-01-08 | 2019-05-10 | 北京信息科技大学 | Raman spectroscopy measurement probe based on fiber bragg grating |
| CN111766228A (en) * | 2020-07-14 | 2020-10-13 | 中国科学院西安光学精密机械研究所 | Non-invasive Raman fiber probe |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1815197A (en) * | 2006-02-24 | 2006-08-09 | 清华大学 | Photon crystal optical-fiber probe sensor based on nano grain surface increasing Raman spectrum |
| WO2015085978A1 (en) * | 2013-12-09 | 2015-06-18 | Friedrich-Schiller-Universität Jena | Device with a raman probe, and method using said device |
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