CN106019469A - Preparation method of coreless optical fiber heavy metal sensor - Google Patents
Preparation method of coreless optical fiber heavy metal sensor Download PDFInfo
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- CN106019469A CN106019469A CN201610601114.0A CN201610601114A CN106019469A CN 106019469 A CN106019469 A CN 106019469A CN 201610601114 A CN201610601114 A CN 201610601114A CN 106019469 A CN106019469 A CN 106019469A
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- optic fibre
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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
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/032—Optical fibres with cladding with or without a coating with non solid core or cladding
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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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention relates to the technical field of low concentration heavy metal ion detection, and particularly relates to a preparation method of a coreless optical fiber heavy metal sensor. The preparation method comprises the following steps that (A) hydrophilic treatment is performed on the surface of the internal wall of a coreless optical fiber by concentrated sulfuric acid and hydrogen peroxide so that the surface of the internal wall of the coreless optical fiber is enabled to contain more hydroxyls; (B) amino propyl triethoxysilane is utilized to perform alcoholysis reaction with the hydroxyls of the surface of the internal wall of the coreless optical fiber so that the surface of the internal wall of the coreless optical fiber is enabled to be aminated; (C) appropriate functional monomers and fluorescein molecules are selected to be coupled; and (D) the formed functional monomers with the fluorescein molecules in the step C are consolidated on the surface of the internal wall of the coreless optical fiber through the amino in the step B. According to the preparation method, the optical fiber sensor convenient for heavy metal detection can be conveniently processed, and online monitoring of heavy metal can be accurately and stably performed by the system.
Description
Technical field
The present invention relates to low-concentration heavy metal ions detection technique field, particularly to a kind of hollow light
The preparation method of fine heavy metal sensor.
Background technology
Along with Chinese Urbanization and industrialized development, it is difficult to metabolism, biology owing to heavy metal has
Enrichment and highly toxic feature, the pollution problem of water environment heavy metal is increasingly by people's
Pay close attention to.And detecting the heavy metal in environment the most accurately and rapidly is problem demanding prompt solution.Closely
The on-line monitoring of heavy metal in environment and the research of the onthe technology of site test of heavy metal in agricultural product over Nian
Although having made some progress, but owing to the content of the heavy metal in environment is the lowest, inspection
Survey difficulty bigger.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of hollow-core fiber heavy metal sensor, carry
The accuracy of detection of high Fibre Optical Sensor heavy metal.
For realizing object above, first technical scheme that the present invention uses is: a kind of hollow-core fiber
The preparation method of heavy metal sensor, comprises the steps: that (A) is by concentrated sulphuric acid and hydrogen peroxide pair
Hollow optic fibre inner wall surface carries out hydrophilic treated makes it contain more hydroxyl；(B) ammonia is then utilized
The hydroxyl generation alcoholysis reaction of propyl-triethoxysilicane and hollow optic fibre inner wall surface makes hollow
Optical fiber inner wall surface amination；(C) suitable function monomer and fluorescein molecule is selected to carry out idol
Close；(D) function monomer with fluorescein molecule formed in step C is passed through in step B
Amino is fixedly arranged at the inner wall surface of hollow optic fibre.
For realizing object above, second technical scheme that the present invention uses is: a kind of hollow-core fiber
The preparation method of heavy metal sensor, comprises the steps: that (A) is by concentrated sulphuric acid and hydrogen peroxide pair
Hollow optic fibre inner wall surface carries out hydrophilic treated makes it contain more hydroxyl；(B) ammonia is then utilized
The hydroxyl generation alcoholysis reaction of propyl-triethoxysilicane and hollow optic fibre inner wall surface makes hollow
Optical fiber inner wall surface amination；(C) select suitable function monomer that hollow optic fibre inner wall surface is entered
Row is modified, and one end of function monomer is fixedly arranged at the inner wall surface of hollow optic fibre by amino；(D) glimmering
Light element molecule is assembled into hollow optic fibre inner wall surface by function monomer.
Compared with prior art, there is techniques below effect in the present invention: by selecting hollow optic fibre,
Fluorescein molecule on combining on the inwall of optical fiber, fluorescein molecule can be with heavy metal to be detected
Reacting thus produce fluorescence, owing to being the fluorescence produced in optical fiber, such fluorescence just can lead to
Crossing fiber-optic transfer out to be gathered by fluorescence spectrophotometer, this sensor construction is simple, preparation is got up non-
Normal convenience.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that mesopore surfaces modifies fluorescein in hollow optic fibre；
Fig. 2 is the schematic diagram at hollow optic fibre inwall processing meso-hole structure；
Fig. 3 is the schematic diagram of Fibre Optical Sensor detection mercury ion.
Detailed description of the invention
Below in conjunction with Fig. 1 to Fig. 3, the present invention is described in further detail.
Refering to Fig. 1, the preparation method of a kind of hollow-core fiber heavy metal sensor, comprise the steps:
(A) by concentrated sulphuric acid and hydrogen peroxide, hollow optic fibre inner wall surface being carried out hydrophilic treated makes it contain
More hydroxyl；(B) aminopropyl triethoxysilane and hollow optic fibre inner wall surface are then utilized
Hydroxyl generation alcoholysis reaction makes hollow optic fibre inner wall surface amination；(C) suitable function is selected
Monomer and fluorescein molecule carry out coupling；(D) by step C formed with fluorescein molecule
Function monomer is fixedly arranged at the inner wall surface of hollow optic fibre by the amino in step B.This preparation method
For embodiment one, in embodiment one, function monomer and fluorescein molecule are first coupled together, so
After be combined in the inner wall surface of hollow optic fibre the most together, be the 1. method shown in arrow in Fig. 1, this
Sample can ensure that the abundant combination of function monomer and fluorescein molecule.
It is, of course, also possible to carried out the combination of fluorescein molecule by another way, embodiment two is such as
The 2. method shown in arrow in Fig. 1, comprises the steps: that (A) is by concentrated sulphuric acid and hydrogen peroxide
Hollow optic fibre inner wall surface carries out hydrophilic treated makes it contain more hydroxyl；(B) then utilize
The hydroxyl generation alcoholysis reaction of aminopropyl triethoxysilane and hollow optic fibre inner wall surface makes to have leisure
Heart optical fiber inner wall surface amination；(C) select suitable function monomer to hollow optic fibre inner wall surface
Modifying, one end of function monomer is fixedly arranged at the inner wall surface of hollow optic fibre by amino；(D)
Fluorescein molecule is assembled into hollow optic fibre inner wall surface by function monomer.In this step, first by merit
Can be attached on hollow optic fibre by monomer, then in conjunction with fluorescence molecule, do so can allow raising merit
Can monomer and the combination effect of hollow optic fibre.
In embodiment one and embodiment two, by selecting hollow optic fibre, the inwall of optical fiber combines
Upper fluorescein molecule, fluorescein molecule can react with heavy metal to be detected thus produce glimmering
Light, owing to being the fluorescence produced in optical fiber, such fluorescence just can be the most glimmering by fiber-optic transfer
Photothermal spectroscopic analyzer is gathered, and this sensor construction is simple, preparation is got up very convenient.According to be checked
The difference of check weighing metal, selects the fluorescein molecule that can react with heavy metal, glimmering further according to this
Light element molecule selects suitable function monomer.As a example by heavy metal Hg, function monomer can select second
Dialdehyde, Biformyl be fixedly arranged at optical fiber surface by amino, the aldehyde radical of other end suspension can be with hat
The amino bonded of the fluorescein molecule that ethers is sensitive to hydrargyrum；Of course, it is possible to use other function list
Body, as acrylamide, isothiocyanic acid carry out surface modification thus fluorescein molecule to different structure
Assemble, thus mercury ion detecting method is optimized.Metal mercury ions shown in Fig. 3
The schematic diagram reacted with fluorescein molecule.
Refering to Fig. 2, the fluorescein molecule number that hollow optic fibre can be combined to is interior with hollow optic fibre
Wall surface amasss relevant, and surface area is the biggest, and the fluorescein molecule that can be combined to is the most, fluorescein molecule
The most, the heavy metal participating in reaction is the most, and the fluorescence of generation is the strongest, and more conducively fluorescence spectrophotometer is entered
Row is analyzed.Whether embodiment one or embodiment two, can go back before described step A
Comprise the steps to be formed meso-hole structure on the inwall of hollow optic fibre: (S1) by concentrated sulphuric acid and
Hydrogen peroxide carries out hydrophilic treated to hollow optic fibre inner wall surface makes it contain more hydroxyl；(S2)
Then the hydroxyl generation alcoholysis utilizing aminopropyl triethoxysilane and hollow optic fibre inner wall surface is anti-
Hollow optic fibre inner wall surface amination should be made；(S3) in hollow optic fibre, polystyrene is added little
Ball, polystyrene sphere bonding action between amino and electrostatic force each other
Under carry out self assembly；(S4) SiO is added2Colloidal sol circulates so that SiO2Only little at polystyrene
The space of ball is formed gel, then removes unnecessary SiO2Colloidal sol；(S5) heating certain time
Or the mode using organic solvent eluting removes polystyrene sphere thus in hollow optic fibre
Meso-hole structure is formed on wall；Described step A～step D, hollow optic fibre inner wall surface replaces to sky
The surface of heart optical fiber inwall meso-hole structure.By forming meso-hole structure on the inwall of hollow optic fibre,
Thus the surface area being significantly increased in hollow optic fibre such that it is able to combine more fluorescein molecule.
Here by first polystyrene sphere being combined on hollow optic fibre inwall, then in the gap of bead
Middle filling SiO2Colloidal sol, final curing SiO2And removing polystyrene sphere, polystyrene sphere is former
The position come just has become room, is formed mesoporous, uses the method to be formed mesoporous very convenient, and
And, various sizes of polystyrene sphere can be selected to form the meso-hole structure of required size.
Preferably, in described step S3, realize poly-by the concentration of regulation polystyrene sphere
Monolayer or the LBL self assembly of styrene bead thus form monolayer in hollow optic fibre inner wall surface
Polystyrene sphere or the polystyrene sphere of multilamellar, and it is dry to carry out low-temperature heat acceleration, should
The temperature range of low temperature is 30 DEG C～80 DEG C.Multi-layer mesoporous structure is provided that bigger surface area；Single
The meso-hole structure of layer is more stable, can select single or multiple lift meso-hole structure according to demand.
Preferably, in described step S4, SiO2Colloidal sol is formed by teos hydrolysis；Shape
Become after gel, by be passed through in hollow optic fibre cyclic nitrogen drying a period of time remove unnecessary
SiO2Colloidal sol.Be passed through nitrogen, have several respects benefit, one, it is possible to by air-flow remove for
SiO2Colloidal sol, they are two years old, it is ensured that hollow optic fibre unimpeded, its three, accelerate SiO2Doing of colloidal sol
Dry solidification.It is of course also possible to select to be passed through other noble gas, as long as it is not involved in reaction
Gas can.
The mode removing polystyrene sphere has a lot, and two ways provided above, one is to add
Heat, another kind is to dissolve.When the mode using heating is removed, it is preferable that described step S5
In, the temperature of heating is 400 DEG C～500 DEG C, and the time of heating is more than 2 hours, the most just can fill
The removal polystyrene sphere divided.When using the mode dissolved, it is preferable that organic solvent can be
Aromatic hydrocarbons (such as benzene, toluene, ethylbenzene, styrene etc.), chlorinated hydrocabon (as carbon tetrachloride, chloroform,
Dichloromethane, chlorobenzene etc.) or esters.
Mesoporous concrete structure, in solution solubility, consumption and each step with added by each step
The parameters such as pressure, temperature, time are the most relevant, can process required by the way of experiment
Meso-hole structure.
Claims (7)
1. a preparation method for hollow-core fiber heavy metal sensor, comprises the steps:
(A) by concentrated sulphuric acid and hydrogen peroxide, hollow optic fibre inner wall surface is carried out hydrophilic treated and make it
Containing more hydroxyl；
(B) hydroxyl of aminopropyl triethoxysilane and hollow optic fibre inner wall surface is then utilized to send out
Raw alcoholysis reaction makes hollow optic fibre inner wall surface amination；
(C) suitable function monomer and fluorescein molecule is selected to carry out coupling；
(D) function monomer with fluorescein molecule formed in step C is passed through in step B
Amino be fixedly arranged at the inner wall surface of hollow optic fibre.
2. a preparation method for hollow-core fiber heavy metal sensor, comprises the steps:
(A) by concentrated sulphuric acid and hydrogen peroxide, hollow optic fibre inner wall surface is carried out hydrophilic treated and make it
Containing more hydroxyl；
(B) hydroxyl of aminopropyl triethoxysilane and hollow optic fibre inner wall surface is then utilized to send out
Raw alcoholysis reaction makes hollow optic fibre inner wall surface amination；
(C) select suitable function monomer that hollow optic fibre inner wall surface is modified, function list
One end of body is fixedly arranged at the inner wall surface of hollow optic fibre by amino；
(D) fluorescein molecule is assembled into hollow optic fibre inner wall surface by function monomer.
3. the preparation method of hollow-core fiber heavy metal sensor as claimed in claim 2, it is special
Levy and be: also comprise the steps before described step A to be formed on the inwall of hollow optic fibre to be situated between
Pore structure:
(S1) by concentrated sulphuric acid and hydrogen peroxide, hollow optic fibre inner wall surface is carried out hydrophilic treated and make it
Containing more hydroxyl；
(S2) hydroxyl of aminopropyl triethoxysilane and hollow optic fibre inner wall surface is then utilized to send out
Raw alcoholysis reaction makes hollow optic fibre inner wall surface amination；
(S3) in hollow optic fibre add polystyrene sphere, polystyrene sphere with amino it
Between bonding action and electrostatic force each other under carry out self assembly；
(S4) SiO is added2Colloidal sol circulates so that SiO2Only in the space of polystyrene sphere
Form gel, then remove unnecessary SiO2Colloidal sol；
(S5) heating certain time or use the mode of organic solvent eluting to remove polystyrene little
Ball thus on the inwall of hollow optic fibre formed meso-hole structure；
Described step A～step D, it is mesoporous that hollow optic fibre inner wall surface replaces to hollow optic fibre inwall
The surface of structure.
4. the preparation method of hollow-core fiber heavy metal sensor as claimed in claim 2, it is special
Levy and be: described function monomer is Biformyl, acrylamide or isothiocyanic acid.
5. the preparation method of hollow-core fiber heavy metal sensor as claimed in claim 3, it is special
Levy and be: in described step S3, realize polyphenyl second by the concentration of regulation polystyrene sphere
Monolayer or the LBL self assembly of alkene bead thus form monolayer polyphenyl in hollow optic fibre inner wall surface
Ethylene bead or the polystyrene sphere of multilamellar, and it is dry to carry out low-temperature heat acceleration, this low temperature
Temperature range be 30 DEG C～80 DEG C.
6. the preparation method of hollow-core fiber heavy metal sensor as claimed in claim 3, it is special
Levy and be: in described step S4, SiO2Colloidal sol is formed by teos hydrolysis；Formed solidifying
After glue, remove unnecessary SiO by being passed through cyclic nitrogen drying a period of time in hollow optic fibre2
Colloidal sol.
7. the preparation method of hollow-core fiber heavy metal sensor as claimed in claim 3, it is special
Levying and be: in described step S5, the temperature of heating is 400 DEG C～500 DEG C, and the time of heating is big
In 2 hours；Organic solvent can be aromatic hydrocarbons, chlorinated hydrocabon or esters.
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| CN201610601114.0A CN106019469B (en) | 2016-07-27 | 2016-07-27 | The preparation method of hollow-core fiber heavy metal sensor |
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| CN201610601114.0A CN106019469B (en) | 2016-07-27 | 2016-07-27 | The preparation method of hollow-core fiber heavy metal sensor |
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|---|---|---|---|---|
| US20020024163A1 (en) * | 2000-06-15 | 2002-02-28 | Em Industries, Inc. | Method for producing sphere-based crystals |
| CN101870866A (en) * | 2010-05-19 | 2010-10-27 | 合肥学院 | Preparation method of inverse opal structure fluorescent thin film for detecting ultra-trace TNT (Trinitrotoluene) steam |
| CN102173602A (en) * | 2011-01-21 | 2011-09-07 | 黄淮学院 | Glass fiber subjected to surface treatment, preparation method and application |
| CN103483612A (en) * | 2013-05-22 | 2014-01-01 | 黄淮学院 | Fluorescent silicon nanoparticle modified optical fiber and preparation method thereof |
| CN204807458U (en) * | 2015-07-14 | 2015-11-25 | 中国计量学院 | Quality of water heavy metal detection device based on quantum dot fluorescence membrane |
-
2016
- 2016-07-27 CN CN201610601114.0A patent/CN106019469B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020024163A1 (en) * | 2000-06-15 | 2002-02-28 | Em Industries, Inc. | Method for producing sphere-based crystals |
| CN101870866A (en) * | 2010-05-19 | 2010-10-27 | 合肥学院 | Preparation method of inverse opal structure fluorescent thin film for detecting ultra-trace TNT (Trinitrotoluene) steam |
| CN102173602A (en) * | 2011-01-21 | 2011-09-07 | 黄淮学院 | Glass fiber subjected to surface treatment, preparation method and application |
| CN103483612A (en) * | 2013-05-22 | 2014-01-01 | 黄淮学院 | Fluorescent silicon nanoparticle modified optical fiber and preparation method thereof |
| CN204807458U (en) * | 2015-07-14 | 2015-11-25 | 中国计量学院 | Quality of water heavy metal detection device based on quantum dot fluorescence membrane |
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