CN106019469B - The preparation method of hollow-core fiber heavy metal sensor - Google Patents
The preparation method of hollow-core fiber heavy metal sensor Download PDFInfo
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- CN106019469B CN106019469B CN201610601114.0A CN201610601114A CN106019469B CN 106019469 B CN106019469 B CN 106019469B CN 201610601114 A CN201610601114 A CN 201610601114A CN 106019469 B CN106019469 B CN 106019469B
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- optic fibre
- wall surface
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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
Abstract
The present invention relates to low-concentration heavy metal ions detection technique fields, in particular to a kind of preparation method of hollow-core fiber heavy metal sensor includes the following steps: that (A) carries out hydrophilic treated to hollow optic fibre inner wall surface by the concentrated sulfuric acid and hydrogen peroxide and it is made to contain more hydroxyl；(B) alcoholysis reaction then occurs using aminopropyl triethoxysilane and the hydroxyl of hollow optic fibre inner wall surface and makes hollow optic fibre inner wall surface amination；(C) suitable function monomer and fluorescein molecule is selected to be coupled；(D) function monomer with fluorescein molecule formed in step C is fixedly arranged to the inner wall surface of hollow optic fibre by the amino in step B.The preparation method can easily process the fibre optical sensor for facilitating detection heavy metal, which can accurately, steadily monitor heavy metal on-line.
Description
Technical field
The present invention relates to low-concentration heavy metal ions detection technique field, in particular to a kind of hollow-core fiber heavy metal sensing
The preparation method of device.
Background technique
With Chinese Urbanization and industrialized development, it is not easy to be metabolized since heavy metal has, bioconcentration and height
The pollution problem of the characteristics of toxicity, water environment heavy metal have been to be concerned by more and more people.And how accurately and rapidly to detect ring
Heavy metal in border is a problem to be solved.Heavy metal shows in the on-line monitoring and agricultural product of heavy metal in environment in recent years
Although field detecting technical research has made some progress, but since the content of the heavy metal in environment is relatively very low, detection
Difficulty of getting up is larger.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of hollow-core fiber heavy metal sensor, improve fibre optical sensor
To the detection accuracy of heavy metal.
In order to achieve the above object, first technical solution that the present invention uses are as follows: a kind of hollow-core fiber heavy metal sensor
Preparation method, include the following steps: that (A) carries out hydrophilic treated to hollow optic fibre inner wall surface by the concentrated sulfuric acid and hydrogen peroxide and make
It contains more hydroxyl；(B) alcohol then occurs using aminopropyl triethoxysilane and the hydroxyl of hollow optic fibre inner wall surface
Solution reaction is so that hollow optic fibre inner wall surface amination；(C) suitable function monomer and fluorescein molecule is selected to be coupled；
(D) function monomer with fluorescein molecule formed in step C is fixedly arranged in hollow optic fibre by the amino in step B
Wall surface.
In order to achieve the above object, second technical solution that the present invention uses are as follows: a kind of hollow-core fiber heavy metal sensor
Preparation method, include the following steps: that (A) carries out hydrophilic treated to hollow optic fibre inner wall surface by the concentrated sulfuric acid and hydrogen peroxide and make
It contains more hydroxyl；(B) alcohol then occurs using aminopropyl triethoxysilane and the hydroxyl of hollow optic fibre inner wall surface
Solution reaction is so that hollow optic fibre inner wall surface amination；(C) suitable function monomer is selected to carry out hollow optic fibre inner wall surface
Modification, one end of function monomer is fixedly arranged at the inner wall surface of hollow optic fibre by amino；(D) fluorescein molecule passes through function monomer
It is assembled into hollow optic fibre inner wall surface.
Compared with prior art, there are following technical effects by the present invention: by selecting hollow optic fibre, on the inner wall of optical fiber
Group closes fluorescein molecule, and fluorescein molecule can react to generate fluorescence with heavy metal to be detected, due to be
The fluorescence generated in optical fiber, such fluorescence can be transmitted out and be acquired by Fluorescence Spectrometer by optical fiber, the sensor structure
Simply, preparation is got up very convenient.
Detailed description of the invention
Fig. 1 is the schematic diagram of the mesopore surfaces modification fluorescein in hollow optic fibre；
Fig. 2 is the schematic diagram in hollow optic fibre inwall processing meso-hole structure；
Fig. 3 is the schematic diagram of fibre optical sensor detection mercury ion.
Specific embodiment
Below with reference to Fig. 1 to Fig. 3, the present invention is described in further detail.
Refering to fig. 1, a kind of preparation method of hollow-core fiber heavy metal sensor, includes the following steps: that (A) passes through the concentrated sulfuric acid
Carrying out hydrophilic treated to hollow optic fibre inner wall surface with hydrogen peroxide makes it contain more hydroxyl；(B) aminopropyl three is then utilized
Ethoxysilane and the hydroxyl of hollow optic fibre inner wall surface occur alcoholysis reaction and make hollow optic fibre inner wall surface amination；(C)
Suitable function monomer and fluorescein molecule is selected to be coupled；(D) function with fluorescein molecule that will be formed in step C
Monomer is fixedly arranged at the inner wall surface of hollow optic fibre by the amino in step B.The preparation method is embodiment one, in embodiment one
In, function monomer and fluorescein molecule are first coupled together, and are then incorporated in the inner wall surface of hollow optic fibre together again, are Fig. 1
In 1. method shown in arrow, doing so can be with the abundant combination of assurance function monomer and fluorescein molecule.
It is, of course, also possible to carry out the combination of fluorescein molecule, the 2. arrow of embodiment two as shown in figure 1 by another way
Shown in method, include the following steps: that (A) carries out hydrophilic treated to hollow optic fibre inner wall surface by the concentrated sulfuric acid and hydrogen peroxide and make
It contains more hydroxyl；(B) alcohol then occurs using aminopropyl triethoxysilane and the hydroxyl of hollow optic fibre inner wall surface
Solution reaction is so that hollow optic fibre inner wall surface amination；(C) suitable function monomer is selected to carry out hollow optic fibre inner wall surface
Modification, one end of function monomer is fixedly arranged at the inner wall surface of hollow optic fibre by amino；(D) fluorescein molecule passes through function monomer
It is assembled into hollow optic fibre inner wall surface.In the step, first function monomer is integrated on hollow optic fibre, then in conjunction with fluorescence point
Son, do so can allow improve function monomer and hollow optic fibre combination effect.
In embodiment one and embodiment two, by selecting hollow optic fibre, group closes fluorescein molecule on the inner wall of optical fiber,
Fluorescein molecule can react to generate fluorescence with heavy metal to be detected, due to being the fluorescence generated in optical fiber,
Fluorescence can be transmitted out and be acquired by Fluorescence Spectrometer by optical fiber in this way, and the sensor structure is simple, preparation is got up very
Convenience.According to the difference of heavy metal to be detected, the fluorescein molecule that can be reacted with heavy metal is selected, further according to the fluorescence
The plain suitable function monomer of molecular selection.By taking heavy metal Hg as an example, function monomer can choose glyoxal, and glyoxal passes through ammonia
Base is fixedly arranged at optical fiber surface, the amino bonded for the fluorescein molecule that the aldehyde radical of other end suspension can be sensitive to mercury with crown ether-like；
Of course, it is possible to using other function monomers, as acrylamide, isothiocyanic acid are surface modified to the glimmering of different structure
Light element molecule is assembled, to optimize to mercury ion detecting method.Metal mercury ions shown in Fig. 3 and fluorescein point
The schematic diagram that son reacts.
Referring to Fig.2, the fluorescein molecule number that hollow optic fibre can be combined to is related with the inner wall surface area of hollow optic fibre,
Surface area is bigger, and the fluorescein molecule that can be combined to is more, and fluorescein molecule is more, and the heavy metal for participating in reaction is more, generates
Fluorescence it is stronger, more conducively Fluorescence Spectrometer is analyzed.Whether embodiment one or embodiment two, can be described
Further include that following steps form meso-hole structure on the inner wall of hollow optic fibre before step A: (S1) passes through the concentrated sulfuric acid and hydrogen peroxide
Carrying out hydrophilic treated to hollow optic fibre inner wall surface makes it contain more hydroxyl；(S2) aminopropyl-triethoxy silicon is then utilized
Alkane and the hydroxyl of hollow optic fibre inner wall surface occur alcoholysis reaction and make hollow optic fibre inner wall surface amination；(S3) in hollow light
Polystyrene sphere, bonding action and mutual electrostatic masterpiece of the polystyrene sphere between amino are added in fibre
Self assembly is carried out under；(S4) SiO is added2Colloidal sol circulates so that SiO2It is only formed in the gap of polystyrene sphere solidifying
Then glue removes extra SiO2Colloidal sol；(S5) it heats certain time or removes polyphenyl by the way of organic solvent elution
Ethylene bead is to form meso-hole structure on the inner wall of hollow optic fibre；Step A~step the D, hollow optic fibre inner wall table
Face is substituted for the surface of hollow optic fibre inner wall meso-hole structure.By forming meso-hole structure on the inner wall of hollow optic fibre, thus greatly
Width increases the surface area in hollow optic fibre, so as to combine more fluorescein molecules.Here by first that polystyrene is small
Ball is incorporated on hollow optic fibre inner wall, then fills SiO in the gap of bead2Colloidal sol, final curing SiO2And remove polyphenyl second
Alkene bead, for the original position of polystyrene sphere just at vacancy, formation is mesoporous, forms mesoporous unusual side using this method
Just, and it is possible to select various sizes of polystyrene sphere to form the meso-hole structure of required size.
Preferably, in the step S3, the concentration by adjusting polystyrene sphere realizes the list of polystyrene sphere
Layer or LBL self assembly are in the polystyrene of hollow optic fibre inner wall surface formation single layer polystyrene sphere or multilayer
Bead, and carry out low-temperature heat and accelerate drying, the temperature range of the low temperature is 30 DEG C~80 DEG C.Multi-layer mesoporous structure can provide more
Big surface area；The meso-hole structure of single layer is more stable, can select single-layer or multi-layer meso-hole structure according to demand.
Preferably, in the step S4, SiO2Colloidal sol is formed by teos hydrolysis；After forming gel, pass through
It is passed through cyclic nitrogen drying into hollow optic fibre and removes extra SiO for a period of time2Colloidal sol.It is passed through nitrogen, there are several respects good
Place, first, can by air-flow remove for SiO2Colloidal sol, secondly, it is ensured that hollow optic fibre it is unimpeded, third, accelerate
SiO2The dry solidification of colloidal sol.It is of course also possible to select to be passed through other inert gases, as long as being not involved in the gas of reaction all
It can be with.
The mode of removal polystyrene sphere has very much, and two ways provided above, one is heating, another kind is molten
Solution.When being removed by the way of heating, it is preferable that in the step S5, the temperature of heating is 400 DEG C~500 DEG C, heating
Time is greater than 2 hours, could adequately remove polystyrene sphere in this way.When by the way of dissolution, it is preferable that organic solvent
Can for aromatic hydrocarbons (such as benzene, toluene, ethylbenzene, styrene), chlorinated hydrocabon (such as carbon tetrachloride, chloroform, methylene chloride, chlorobenzene) or
Esters.
Mesoporous specific structure, in solution solubility added in each step, dosage and each step pressure, temperature, when
Between etc. parameters it is all related, required meso-hole structure can be processed by way of experiment.
Claims (6)
1. a kind of preparation method of hollow-core fiber heavy metal sensor, includes the following steps:
(A) carrying out hydrophilic treated to hollow optic fibre inner wall surface by the concentrated sulfuric acid and hydrogen peroxide makes it contain more hydroxyl；
(B) then made using aminopropyl triethoxysilane and the hydroxyl of hollow optic fibre inner wall surface generation alcoholysis reaction hollow
Optical fiber inner wall surface amination；
(C) suitable function monomer and fluorescein molecule is selected to be coupled, the function monomer is glyoxal, acrylamide
Or isothiocyanic acid；
(D) function monomer with fluorescein molecule formed in step C is fixedly arranged at hollow optic fibre by the amino in step B
Inner wall surface.
2. a kind of preparation method of hollow-core fiber heavy metal sensor, includes the following steps:
(A) carrying out hydrophilic treated to hollow optic fibre inner wall surface by the concentrated sulfuric acid and hydrogen peroxide makes it contain more hydroxyl；
(B) then made using aminopropyl triethoxysilane and the hydroxyl of hollow optic fibre inner wall surface generation alcoholysis reaction hollow
Optical fiber inner wall surface amination；
(C) suitable function monomer is selected to modify hollow optic fibre inner wall surface, one end of function monomer is solid by amino
The inner wall surface in hollow optic fibre is tied, the function monomer is glyoxal, acrylamide or isothiocyanic acid；
(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 characterised in that: the step A
Before further include that following steps form meso-hole structure on the inner wall of hollow optic fibre:
(S1) carrying out hydrophilic treated to hollow optic fibre inner wall surface by the concentrated sulfuric acid and hydrogen peroxide makes it contain more hydroxyl；
(S2) alcoholysis reaction then occurs using aminopropyl triethoxysilane and the hydroxyl of hollow optic fibre inner wall surface makes to have leisure
Heart optical fiber inner wall surface amination；
(S3) polystyrene sphere, bonding action and phase of the polystyrene sphere between amino are added in hollow optic fibre
Self assembly is carried out under electrostatic force between mutually；
(S4) SiO is added2Colloidal sol circulates so that SiO2Gel is only formed in the gap of polystyrene sphere, is then removed
Extra SiO2Colloidal sol；
(S5) it heats certain time or removes polystyrene sphere by the way of organic solvent elution in hollow optic fibre
Inner wall on form meso-hole structure；
Step A~step the D, hollow optic fibre inner wall surface are substituted for the surface of hollow optic fibre inner wall meso-hole structure.
4. the preparation method of hollow-core fiber heavy metal sensor as claimed in claim 3, it is characterised in that: the step S3
In, the concentration by adjusting polystyrene sphere realizes single layer or the LBL self assembly of polystyrene sphere in hollow light
Fine inner wall surface forms the polystyrene sphere of single layer polystyrene sphere or multilayer, and carries out low-temperature heat and accelerate drying,
The temperature range of the low temperature is 30 DEG C~80 DEG C.
5. the preparation method of hollow-core fiber heavy metal sensor as claimed in claim 3, it is characterised in that: the step S4
In, SiO2Colloidal sol is formed by teos hydrolysis；After forming gel, by being passed through cyclic nitrogen drying into hollow optic fibre
A period of time removes extra SiO2Colloidal sol.
6. the preparation method of hollow-core fiber heavy metal sensor as claimed in claim 3, it is characterised in that: the step S5
In, the temperature of heating is 400 DEG C~500 DEG C, and the time of heating is greater than 2 hours；Organic solvent is aromatic hydrocarbons, chlorinated hydrocabon or esters.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1292727A2 (en) * | 2000-06-15 | 2003-03-19 | MERCK PATENT GmbH | A method for producing sphere-based crystals |
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- 2016-07-27 CN CN201610601114.0A patent/CN106019469B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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