CN113433083A - Method for detecting ammonia concentration in water by combining active microsphere cavity and phenol red - Google Patents
Method for detecting ammonia concentration in water by combining active microsphere cavity and phenol red Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000004005 microsphere Substances 0.000 title claims abstract description 69
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 37
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
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- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 2
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- 239000002696 acid base indicator Substances 0.000 description 1
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- FFUMCSDSJNSMQH-HEXQVDJKSA-K chromoxane cyanin R Chemical compound [Na+].[Na+].[Na+].C1=C(C([O-])=O)C(=O)C(C)=C\C1=C(C=1C(=CC=CC=1)S([O-])(=O)=O)\C1=CC(C)=C(O)C(C([O-])=O)=C1 FFUMCSDSJNSMQH-HEXQVDJKSA-K 0.000 description 1
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- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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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
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/24—Coupling light guides
- G02B6/255—Splicing of light guides, e.g. by fusion or bonding
- G02B6/2551—Splicing of light guides, e.g. by fusion or bonding using thermal methods, e.g. fusion welding by arc discharge, laser beam, plasma torch
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/24—Coupling light guides
- G02B6/255—Splicing of light guides, e.g. by fusion or bonding
- G02B6/2552—Splicing of light guides, e.g. by fusion or bonding reshaping or reforming of light guides for coupling using thermal heating, e.g. tapering, forming of a lens on light guide ends
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Abstract
The invention provides a method for detecting ammonia concentration in water by combining an active microsphere cavity and phenol red, which comprises the following steps: preparing an integrated structure of the hollow optical fiber built-in rare earth ion doped microsphere resonator; (1) preparing an optical fiber structure with built-in gain microspheres; (2) preparing erbium-ytterbium co-doped lead-containing glass microspheres; (3) placing the microsphere inside the optical fiber; step two: the detection of the ammonia concentration in the water is realized based on the integrated structure; according to the invention, the rare earth ion doped microsphere cavity is used for replacing a composite material film, so that a complex film synthesis process is avoided, the microsphere cavity is integrated in the optical fiber for packaging, the compactness of the sensing element is greatly improved, meanwhile, the microsphere cavity is more conveniently connected with detection devices such as a light source and a spectrometer, and the test system of the whole sensor is optimized. On the basis of improving the practicality of sensor, promoted the sensing performance more, possessed higher sensitivity and selectivity, faster response and recovery time, and possessed outstanding stability and repeatability.
Description
Technical Field
The invention relates to a method for detecting ammonia concentration in water, in particular to a method for detecting ammonia concentration in water by combining an active microsphere cavity and phenol red.
Background
The aqueous ammonia being ammonia (NH)3) The aqueous solution is an important chemical raw material in the world, and is widely applied to the manufacturing industries of petroleum smelting, fertilizer manufacturing, medicines, plastics, dyes and the like. However, ammonia gas content in ammonia waterWeak hydrolysis of the ion to generate hydroxyl ion and ammonium ion (NH)4 +) On the one hand, too high a concentration of NH4 +The water body is eutrophicated, and the water body is anoxic due to the massive growth of algae, so that the ecological balance of the water system is finally destroyed; on the other hand, human beings receive NH when ingested4 +Contaminated food or water can cause erosion of the mouth, esophagus and stomach, and if high ammonia is inhaled, reflex respiratory arrest and cardiac arrest can result. Therefore, there is a need for sensitive, selective instruments for the detection of such substances. The method for detecting the concentration of ammonia in water mainly comprises an electrochemical analysis method, an instrumental analysis method, a spectrophotometric analysis method and other analysis technologies (a fluorescence method). Taking an ion selective electrode method as an example, the ammonium ion electrode method refers to that according to the Nernst principle, by means of a sensitive membrane, the specific response of ammonium ions can be realized, the potential of the inner part and the outer part of the sensitive membrane is changed, and the ammonia nitrogen analysis of a detected water sample is realized. According to data display, data errors can be controlled within 0.5% by the measuring result of the ion selective electrode method, so that the sensitivity is very high, and the operation difficulty is relatively low; taking the kjeldahl method as an example, the kjeldahl method is based on the principle that an excessive sodium hydroxide solution is directly injected into a measured water sample without digestion, the sodium hydroxide solution is gradually converted into alkalescence from strong basicity, and ammonium salt in water is converted into ammonia. After distillation and evolution of ammonia, absorption was carried out by means of a boric acid solution, which was then titrated using a potentiometric titrator. After the boric acid absorbs ammonia, the alkalinity of the boric acid is gradually enhanced, then a sulfuric acid solution is used for titration to an original pH value, a pH meter is used for controlling a titration end point, and the ammonia nitrogen content in water is analyzed by depending on the usage amount of sulfuric acid in the link; the spectrophotometric analysis method mainly comprises a Nashin reagent method, a salicylic acid-hypochlorite method, a starch blue spectrophotometric method and the like. The principle of the indophenol blue photometry is as follows: the ammonium nitrogen in the water interacts with phenol and sodium hypochlorite in a strong alkaline environment, so that the water-soluble fuel indophenol blue with strong stability is formed. Experiments show that if the ammonia nitrogen concentration in the tested water body sample is 0.01-0.5mg/L, the absorbance is in direct proportion to the ammonium nitrogen contentContrast measurements can be made at the 625nm position; the principle of fluorescence is to utilize the characteristic that some substances can generate fluorescence under the irradiation of ultraviolet rays, such as: in an alkaline substance environment, the o-phthalaldehyde reacts with the nitrogen ammonia to form a substance with a fluorescence characteristic, and the generated fluorescence intensity and the ammonia nitrogen mass concentration are in a linear relation of 2-300 mu g/L, so that the data of the ammonia nitrogen content in the water body to be detected can be obtained by detecting the fluorescence intensity.
In addition, researchers find that on the basis of a light absorption method, functions of in-situ and real-time rapid analysis and the like can be achieved by utilizing the characteristics of fluorescent dye, and the sensing performance of the ammonia concentration detector in water is improved. The fluorescent dye has high extinction coefficient, wide absorption band and high fluorescence quantum yield, not only shows obvious absorption and fluorescence intensity change after the fluorescent dye acts on a specific analyte, but also can realize functions of naked eye detection and the like along with obvious color change.
Currently, some progress and effort has been made in the study of fluorescent dyes based on the field of ammonia sensing applications. For example, a dye-doped polypyrrole film for ammonia gas sensing is prepared by doping chrome cyanine R in polypyrrole, and can show a significant absorbance change after being exposed to ammonia gas with different concentrations at room temperature, and has a fast response time and a lower detection limit; a composite material film synthesized by ethyl cellulose and oxazine 170 perchlorate is used as a sensing element, and the fluorescence intensity ratio of the oxazine 170 perchlorate at 565nm and 630nm can be changed under different ammonia water concentrations, so that ammonia detection and the like can be realized. However, the layer-by-layer self-assembly composite film is complicated in preparation process, difficult to integrate with a testing device and the like, and further development in actual production and living scenes is limited.
The rare earth ion doped glass material is a good luminescent substrate material, can realize the fluorescent radiation of visible light, near infrared and intermediate infrared bands by adjusting the species of the doped rare earth ions, and is widely appliedIn laser, optical amplifier, optical communication, etc. The main absorption wavelengths of the multiple fluorescent dyes are all in the visible light band, which provides a possibility for the rare earth ion doped glass material and the fluorescent dyes to be combined and applied to the detection of the ammonia concentration in water. Phenol red, aTriphenylmethaneThe organic reagent is usually combined with other dyes to form a multi-element complex system, and is applied to trace elements by a fading spectrophotometry. Phenol red does not have the fluorescence luminescence property, however, when the phenol red is in an environment with an increasingly higher pH value, the main absorption wavelength of the phenol red shifts, and the phenol red is shifted from 460nm to 560nm, so that the phenol red has stronger absorption to green light, and the phenol red also changes color to play a role of an acid-base indicator. Then, if the rare earth glass material is combined with the phenol red, the glass material is exposed in the ammonia water on the premise of obtaining the visible light green fluorescence radiation of the glass material, and the ammonia water is a weak base, so that the pH value of the environment is increased, the phenol red starts to absorb the green light, the intensity of the green light is reduced, and the detection of the ammonia concentration in the water can be realized by monitoring the change of the intensity of the green light. The use of composite material films is avoided, the preparation process of the sensing element is simplified, and the rare earth glass material can also be processed into optical fibers, glass microsphere cavities and other elements, so that the optical fibers, the glass microsphere cavities and other elements can be conveniently connected with other photoelectric devices, a testing device is more compact, the application performance of the sensor is optimized on the whole, and the sensor has a good development prospect.
Disclosure of Invention
The invention aims to provide a method for detecting the ammonia concentration in water by combining an active microsphere cavity and phenol red, aiming at realizing the detection of the ammonia concentration in water.
The purpose of the invention is realized as follows:
a method for detecting the concentration of ammonia in water by combining an active microsphere cavity with phenol red comprises the following steps:
the method comprises the following steps: preparing an integrated structure of the hollow optical fiber built-in rare earth ion doped microsphere resonator;
(1) optical fiber structure for preparing built-in gain microspheres
Welding a single mode fiber-multimode fiber-suspended three-core hollow special fiber structure, wherein the length of the multimode fiber is 2mm, and the length of the suspended three-core hollow special fiber is 0.5 mm; tapering the hollow optical fiber, wherein the diameter of the taper waist is 30 mu m;
(2) preparing erbium-ytterbium co-doped lead-containing glass microspheres;
the formula of the multi-component glass comprises the following components: 72TeO2-20ZnO-5Na2CO3–1.5Y2O3–0.5Er2O3–1Yb2O3(ii) a Weighing 30g of high-purity powdery raw material according to the formula of the components, and fully and uniformly mixing in an agate mortar; pouring the uniformly mixed materials into a 20ml corundum crucible, and melting for 30min in a muffle furnace at 900 ℃; then pouring the glass melt into a preheated stainless steel mold, annealing for 3 hours, and then slowly cooling to room temperature to reduce residual internal stress; grinding the prepared lead-containing glass into powder, screening the powder by a 500-mesh sieve into finer powder and dispersing the powder; pouring the powder into an electric furnace filled with high-purity nitrogen, setting the temperature at 800 ℃, setting the gas flow rate at 2L/min, and placing a culture dish filled with deionized water at the bottom of the electric furnace to collect microspheres; closing the air valve after 30s, evaporating deionized water in the culture dish, transferring the microspheres onto a glass slide, and observing the morphology of the microspheres under a microscope;
(3) placing microspheres inside an optical fiber
Drawing a single-mode fiber by using a drawing cone platform, wherein the diameter of the cone waist is 30 mu m, and cutting off the single-mode fiber in the middle to prepare a half-drawing cone fiber; placing the welded single-mode fiber-multimode fiber-suspended three-core hollow special fiber structure in the step 1 on a three-dimensional adjusting platform and fixing the structure by using a fiber clamp; adsorbing the microspheres prepared in the step 2 at the front end of the optical fiber by using a half-tapered optical fiber, placing the optical fiber on another three-dimensional adjusting platform, and fixing the optical fiber by using an optical fiber clamp; under the observation of a microscope, adjusting the three-dimensional platform, and placing the microspheres in the hollow optical fiber; welding the other end of the hollow optical fiber with the built-in microspheres with a multimode optical fiber-single mode optical fiber structure to prepare a single mode optical fiber-multimode optical fiber-suspended three-core hollow special optical fiber-multimode optical fiber-single mode optical fiber structure to finish packaging;
step two: the detection of the ammonia concentration in the water is realized based on the integrated structure;
placing a single-mode fiber-multimode fiber-suspended three-core hollow special fiber-multimode fiber-single-mode fiber structure with microspheres in a transparent sealing box, and immersing the structure into a phenol red solution at the bottom of the sealing box; a small hole is drilled at the top of the sealing box, and the size of the hole is matched with the diameter of the dropper; then adhering the dropper on the sealing box by using a two-component epoxy adhesive, filling a gap between the dropper and the hole and ensuring the sealing property; er3 pumped by 980nm laser diode+-Yb3+Co-doping tellurate glass microspheres; coupling pump light into the microspheres through the suspended core inside the hollow optical fiber, and observing green and red up-conversion fluorescence emission; in order to avoid the influence of liquid level change, an optical probe of a micro spectrometer is arranged below the sealing box, the up-conversion fluorescence of the microspheres is collected, and the collected signals are processed by computer analysis software to obtain an emission spectrum; the ammonia water solution is continuously added through the dropper, the pH value of the solution is increased along with the increase of the ammonia concentration, the absorption peak of phenol red is transferred, the green light of the microsphere is strongly absorbed, the ratio of the up-conversion green light to the red light is changed, and the detection of the ammonia concentration is realized.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the rare earth ion doped microsphere cavity is used for replacing a composite material film, so that a complex film synthesis process is avoided, the microsphere cavity is integrated in the optical fiber for packaging, the compactness of the sensing element is greatly improved, meanwhile, the microsphere cavity is more conveniently connected with detection devices such as a light source and a spectrometer, and the test system of the whole sensor is optimized. On the basis of improving the practicality of sensor, promoted the sensing performance more, possessed higher sensitivity and selectivity, faster response and recovery time, and possessed outstanding stability and repeatability.
(2) The invention is combined with the phenol red indicator, the up-conversion luminescence of the rare earth ion doped microsphere cavity is applied to ammonia sensing for the first time, the excellent sensing characteristic is shown, the application field of the up-conversion luminescence material is expanded, the members of the optical ammonia sensor are enriched, and a new example is injected for interdisciplinary development.
(3) The invention can realize quick response to the change of the ammonia concentration in water, and the detector has good stability and repeatability and can cope with complex practical application environment.
Drawings
FIG. 1 is an illustration of the preparation of erbium ytterbium co-doped tellurate glass microspheres;
FIG. 2 is a photomicrograph of the prepared glass microspheres of regular size;
FIG. 3 is a structural schematic of a hollow optical fiber built-in glass microsphere resonator;
FIG. 4 is a microsphere up-conversion fluorescence spectrum at different ammonia concentrations;
FIG. 5 shows the fluorescence intensity ratio (I)547/I659) Fitting as the ammonia concentration in water changes.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention relates to a hollow optical fiber built-in rare earth ion doped microsphere resonator integrated structure, which is combined with phenol red dye to realize the detection of ammonia concentration in water. The method mainly comprises the following two aspects:
1. preparing an integrated structure of the hollow optical fiber built-in rare earth ion doped microsphere resonator:
(1) optical fiber structure for preparing built-in gain microspheres
And welding a single mode fiber-multimode fiber-suspended three-core hollow special fiber structure, wherein the length of the multimode fiber is 2mm, and the length of the suspended three-core hollow special fiber is 0.5 mm. The hollow fiber was tapered with a taper waist diameter of 30 μm.
(2) Preparation of erbium-ytterbium co-doped lead-containing glass microspheres
The formula of the multi-component glass comprises the following components: 72TeO2-20ZnO-5Na2CO3–1.5Y2O3–0.5Er2O3–1Yb2O3. Weighing 30g of high-purity powdery raw material according to the formula of the components, and fully and uniformly mixing the raw material in an agate mortar. The uniformly mixed material was poured into a 20ml corundum crucible and melted in a muffle furnace at 900 ℃ for 30 min. Then pouring the glass melt into a preheated stainless steel moldAnd annealing for 3h, and then slowly cooling to room temperature to reduce residual internal stress. The prepared lead-containing glass was ground into powder and sieved through a 500 mesh sieve to obtain finer powder and dispersed. Pouring the powder into an electric furnace filled with high-purity nitrogen, setting the temperature at 800 ℃, setting the gas flow rate at 2L/min, and placing a culture dish filled with deionized water at the bottom of the electric furnace to collect microspheres. After 30s, the air valve is closed, deionized water in the culture dish is evaporated, the microspheres are transferred onto a glass slide, and the morphology of the microspheres is observed under a microscope.
(3) The microspheres are placed inside the optical fiber.
And drawing the single-mode optical fiber by using a drawing cone platform, wherein the diameter of the cone waist is 30 mu m, and cutting off the single-mode optical fiber in the middle to prepare the semi-drawing cone optical fiber. And (3) placing the welded single-mode fiber-multimode fiber-suspended three-core hollow special fiber structure in the step (1) on a three-dimensional adjusting platform and fixing the structure by using a fiber clamp. And (3) adsorbing the microspheres prepared in the step (2) at the front end of the optical fiber by using a half-tapered optical fiber, placing the optical fiber on another three-dimensional adjusting platform, and fixing the optical fiber by using an optical fiber clamp. Under the observation of a microscope, the three-dimensional platform is adjusted, and the microspheres are placed inside the hollow optical fibers. And welding the other end of the hollow optical fiber with the built-in microspheres with a multimode optical fiber-single mode optical fiber structure to prepare a single mode optical fiber-multimode optical fiber-suspended three-core hollow special optical fiber-multimode optical fiber-single mode optical fiber structure, and finishing packaging.
2. Detection of ammonia concentration in water based on integrated structure
The structure of the single mode fiber, the multimode fiber, the suspended three-core hollow special fiber, the multimode fiber and the single mode fiber with the built-in microspheres is placed in a transparent sealing box and is immersed in phenol red solution at the bottom of the sealing box. A small hole is drilled at the top of the sealing box, and the size of the hole is matched with the diameter of the dropper. Then the dropper is stuck on the sealing box by using a double-component epoxy adhesive, so that the gap between the dropper and the hole is filled, and the sealing property is ensured. Pumping Er3 with 980nm laser diode (MCSPL-980, MC fiber, China)+-Yb3+Co-doping tellurate glass microspheres. The pump light was coupled into the microsphere through the inner suspended core of the hollow fiber and green and red up-converted fluorescence emission was observed. To avoid the influence of liquid level variation, under a sealed boxAn optical probe of a micro spectrometer (USB4000, Ocean Optics, China) is installed, the up-conversion fluorescence of the microspheres is collected, and the collected signals are processed by computer analysis software (Ocean Optics) to obtain an emission spectrum. The ammonia water solution is continuously added through the dropper, the pH value of the solution is increased along with the increase of the ammonia concentration, the absorption peak of phenol red is transferred, the green light of the microsphere is strongly absorbed, the ratio of the up-conversion green light to the red light is changed, and the detection of the ammonia concentration is realized.
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Application publication date: 20210924 |