CN105349150A - Fluorescent film sensing composite material as well as preparation method and application thereof - Google Patents
Fluorescent film sensing composite material as well as preparation method and application thereof Download PDFInfo
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- CN105349150A CN105349150A CN201510943978.6A CN201510943978A CN105349150A CN 105349150 A CN105349150 A CN 105349150A CN 201510943978 A CN201510943978 A CN 201510943978A CN 105349150 A CN105349150 A CN 105349150A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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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 invention relates to a fluorescent film sensing composite material as well as a preparation method and application thereof, belonging to the field of fluorescent film sensing materials. The material comprises conductive glass, photonic crystals and quantum dots, wherein the photonic crystals cover the surface of the conductive glass to form a photonic crystal film; the quantum dots are self-assembled on the surface of the photonic crystal film to form a quantum dot film; and emission peaks of the quantum dots are in the ranges of photonic band gaps of the photonic crystals. The fluorescent film sensing composite material has the beneficial effects that the fluorescent film sensing composite material has the characteristics of good water resistance, low possibility in falling off of fluorescent films, high sensitivity, and the like.
Description
Technical field
The present invention relates to a kind of fluorescence membrane sensing composite material and its preparation method and application, belong to fluorescence membrane sensing material field.
Background technology
Along with the enhancing of people's environmental consciousness, the pollution of the heavy metal ion in environment and sanitary sewage is also more and more paid attention to, especially Pb
2+, Hg
2+, Cd
2+, Cu
2+and the significant heavy metal element of bio-toxicity such as metallic arsenic is to the pollution of water body.Do not reach GB8978-1669 " integrated wastewater discharge standard " and just directly entered in river, lake or ocean after the unprocessed for some reason or process of heavy metal ion, it is finally made to be polluted, because they can not be biodegradable, contrary can enrichment under the biological magnification of food chain, finally enter human body.Heavy metal in human body can and protein and some enzyme there is strong interaction; make them lose activity, also may accumulate in some organ in human body, cause chronic poisoning; therefore before discharge, it is measured for human health and environment protection, all there is positive meaning.
At present, homogeneous fluorescent sensing material, because having the characteristics such as highly sensitive, selectivity is good, obtains important application, attracts widespread attention in the selective enumeration method of metal ion, negatively charged ion and neutral molecule etc.But what homogeneous fluorescent sensing material existed be difficult to device, can only single use and be easy to pollute the shortcomings such as system to be measured, applies because which limit it.
Such as quantum dot is owing to having excellent optical property, as wide in absorbing wavelength and continuously, fluorescence emission peak is tunable, and fluorescence lifetime is long, shows wide application prospect in the field such as fluorescence imaging and biomarker.Current quantum dot mainly builds various chemistry or bio-sensing system with colloid form, and forms homogeneous phase with detected solion, thus detects ion.But because quantum dot and ionic interaction major part are non-reversible, thus the use determining quantum dot is all disposable, cannot recycle, cause environmental pollution again while waste.
In order to solution must not reusable problem, Liu Meng. based on chemical-biological sensing novel method and the environmental applications research (Ph.D. Dissertation) of quantum dot and Graphene. Dalian University of Technology, 2012. achieve CdTe quantum effectively fixing in conductive glass substrate by LBL self-assembly technique, thus the fluorescence membrane sensing material made based on quantum dot, and establish a kind of fluoroscopic examination heavy metal Cu
2+method, this fluorescence membrane sensing material is after reusing four times, and fluorescence can return to original more than 95%, thus avoids the shortcoming that cannot recycle that homogeneous phase quantum dot exists in ion detection.But because the quantum dot of preparation is wetting ability, the poor water resistance when detecting aqueous solution metal ion, and then cause fluorescence membrane to come off problem, work-ing life is very short, but also deterioration of sensitivity, selectivity step-down problem can be caused, limit it and further develop and apply.
Summary of the invention
The present invention, by adding photon crystal film layer in existing fluorescence membrane sensing composite material, solves the problems referred to above.
The invention provides a kind of fluorescence membrane sensing composite material, described material comprises conductive glass, photonic crystal, quantum dot; Described photonic crystal is covered on conductive glass surface and forms photon crystal film, described quantum dot photon crystal film on the surface self-assembly form quantum dot film, the emission peak of described quantum dot is within the scope of the forbidden photon band of photonic crystal.
Photonic crystal of the present invention is preferably by least one in the photonic crystal of silicon dioxide microsphere, polystyrene microsphere, polyethylene microballoon, polypropylene microballoon, methyl methacrylate microballoon, polyacrylonitrile microballoon, poly-(styrene methyl methacrylate-vinylformic acid) microballoon self-assembly, and the microspherulite diameter that described self-assembly forms photonic crystal is 100 ~ 500nm.
Quantum dot of the present invention is preferably formed by cadmium telluride, Cadmium Sulfide, cadmium selenide, zinc sulphide, zinc selenide or zinc telluridse self-assembly.
Quantum dot of the present invention is preferably the quantum dot that mercaptan carboxylic acid modifies.
Mercaptan carboxylic acid of the present invention is preferably Thiovanic acid, 2 mercaptopropionic acid or 3-thiohydracrylic acid.
Another order of the present invention is to provide the preparation method of above-mentioned fluorescence membrane sensing composite material, and described preparation method comprises the steps:
1. insert conductive glass vertical component for the preparation of in the microspheres solution of photonic crystal, 45 ~ 65 DEG C of reaction 10 ~ 20h, obtain the photon crystal film being covered in conductive glass surface;
2. by step 1. products obtained therefrom be vertically immersed in silane coupler solution, dry, be more vertically immersed in water-soluble quantum dot that mercaptan carboxylic acid modifies, dry, obtain fluorescence membrane sensing composite material;
Or by step 1. products obtained therefrom be vertically immersed in silane coupler solution, dry, more repeatedly repeated vertical is immersed in step in the water-soluble quantum dot that mercaptan carboxylic acid modifies and dry, obtains fluorescence membrane sensing composite material.
Silane coupling agent of the present invention preferably has amino silane coupling agent, at least one more preferably in 3-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane and N-β-aminoethyl-γ-aminopropyltrimethoxysilane.
Silane coupler solution of the present invention is preferably 0.5 ~ 2wt% silane coupling agent ethanol solution.
The preparation method of the water-soluble quantum dot that mercaptan carboxylic acid of the present invention modifies comprises the steps:
1. tellurium powder, sodium borohydride and water are mixed, under inert ambient environment, 25 ~ 40 DEG C of reaction 1 ~ 4h, obtain quantum dot precursor liquid;
2. Cadmium chloride fine powder is water-soluble, add mercaptan carboxylic acid, sodium hydroxide solution successively, letting nitrogen in and deoxidizing, add step 1. products obtained therefrom, 60 ~ 90 DEG C of hydro-thermal reaction 9 ~ 18h, obtain the water-soluble quantum dot that mercaptan carboxylic acid modifies.
The mol ratio of tellurium powder of the present invention, sodium borohydride, Cadmium chloride fine powder and mercaptan carboxylic acid is preferably 1:(20 ~ 60): (15 ~ 45): (6 ~ 15).
Another order of the present invention is to provide the application of above-mentioned fluorescence membrane sensing composite material on detection metal ion in solution content.
Metal ion of the present invention is preferably Cu
2+, Hg
2+, Fe
3+and Ag
+.
Fluorescence membrane sensing composite material is preferably immersed in metal ion solution by application method of the present invention, dry, measures its fluorescence intensity, obtains metal ion solution concentration.
Beneficial effect of the present invention is:
1. fluorescence membrane sensing composite material of the present invention achieves photonic crystal and quantum dot fixing successively on conductive glass, the specific surface area that photon crystal film is huge makes the increase of quantum dot deposition, and the Bragg diffraction of photonic crystal can significantly improve again the fluorescence intensity of quantum dot, namely utilize photonic crystal in the range of frequency of forbidden photon band, light can not through and by the character reflected, in order to strengthen the fluorescence intensity of quantum dot, greatly improve response and the selectivity of fluorescence membrane sensing composite material heavy metal cupric ion, and achieve fluorescence membrane sensing composite material reusing in heavy metal copper ion detection,
2. the photonic crystal growth time being covered in the photon crystal film preparation method of conductive glass surface of the present invention greatly foreshortens to 12h, and the photon crystal film growing 1cm in prior art needs 3 ~ 4d;
3. the present invention adopts silane coupling agent photonic crystal and quantum dot, quantum dot is firmly fixed on photon crystal surface, improve the performances such as the anti-aging of quantum dot and physical strength, prevent coming off of quantum dot, achieve the stable of fluorescence membrane sensing composite material to reuse, improve the work-ing life of fluorescence membrane sensing composite material;
4. fluorescence membrane sensing composite material of the present invention, when quantum dot is finishing Thiovanic acid, free carboxylic acid on sulfydryl can carry out covalently bound with having amino silane coupling agent, not only quantum dot firmly can be fixed on photon crystal surface, free carboxylic acid on hydrophilic sulfydryl can also be linked into hydrophobic molecular chain-end, improve the water tolerance of quantum dot, make quantum dot film difficult drop-off and be dissolved in detection solvent, thus forming stable laminated film.
Accompanying drawing explanation
Accompanying drawing 6 width of the present invention,
Fig. 1 is the polystyrene microsphere photon crystal film scanning electron microscope (SEM) photograph being covered in conductive glass surface that embodiment 1 obtains;
Fig. 2 is the effect diagram of metal ion to the fluorescence membrane sensing composite material fluorescence intensity that embodiment 1 obtains;
Fig. 3 is that the fluorescence membrane sensing composite material that obtains of embodiment 1 is to different concns Cu
2+fluorescence response spectrum and Cu
2+the graph of a relation of concentration;
Fig. 4 is that the fluorescence membrane sensing composite material that obtains of embodiment 1 is to different concns Cu
2+fluorescence intensity and Cu
2+the graph of a relation of concentration;
Fig. 5 is that the existing fluorescence membrane sensing composite material that obtains of comparative example 1 is to different concns Cu
2+fluorescence response spectrum and Cu
2+the graph of a relation of concentration;
Fig. 6 is that the existing fluorescence membrane sensing composite material that obtains of comparative example 1 is to different concns Cu
2+fluorescence intensity and Cu
2+the graph of a relation of concentration.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
The pretreatment process of following embodiment and comparative example conductive glass used is the conductive glass of 2cm × 1.5cm × 0.5cm is placed in respectively successively dilute hydrochloric acid, dehydrated alcohol, each ultrasonic cleaning 15min of deionized water, dry.
2mg tellurium powder, 24mg sodium borohydride and 2mL high purity water mix by the preparation method of following embodiment and comparative example quantum dot precursor liquid used, in a nitrogen environment 32 DEG C of reaction 2h.
Embodiment 1
A preparation method for fluorescence membrane sensing composite material, described preparation method comprises the steps:
1. the water-soluble poly phenylethylene micro ball being 240nm by 300 μ L particle diameters joins in 5mL deionized water, ultrasonic vibration 30min, conductive glass vertical component is inserted in the water-soluble poly phenylethylene micro ball aqueous solution, 55 DEG C of reaction 12h, obtain the polystyrene microsphere photon crystal film being covered in conductive glass surface, its pattern is shown in accompanying drawing 1;
2. 100mg Cadmium chloride fine powder is dissolved in 100mL high purity water, adds the 2mol/L sodium hydroxide solution of 21.7mg Thiovanic acid, 5mL successively, letting nitrogen in and deoxidizing 30min, add 1mL quantum dot precursor liquid, 80 DEG C of hydro-thermal reaction 12h, obtain the cadmium telluride solution that Thiovanic acid is modified; By step 1. products obtained therefrom be vertically immersed in the 3-aminopropyl triethoxysilane ethanol solution of 1wt% and activate 30min, dry, vertically be immersed in 1h in the cadmium telluride solution of Thiovanic acid modification, dry, repeat vertically to be immersed in for 4 times 1h and dry step in the cadmium telluride solution that Thiovanic acid modifies again, obtain the fluorescence membrane sensing composite material of 5 layers of quantum dot.
Embodiment 2
A preparation method for fluorescence membrane sensing composite material, described preparation method comprises the steps:
1. the silicon dioxide microsphere being 240nm by 300 μ L particle diameters joins in 5mL deionized water, ultrasonic vibration 30min, inserted by conductive glass vertical component in the silicon dioxide microsphere aqueous solution, 55 DEG C of reaction 12h, obtain the silicon dioxide microsphere photon crystal film being covered in conductive glass surface;
2. 100mg Cadmium chloride fine powder is dissolved in 100mL high purity water, add the 2mol/L sodium hydroxide solution of 25.0mg3-thiohydracrylic acid, 5mL successively, letting nitrogen in and deoxidizing 30min, add 1mL quantum dot precursor liquid, 80 DEG C of hydro-thermal reaction 3h, obtain the cadmium telluride solution that 3-thiohydracrylic acid is modified; By step 1. products obtained therefrom be vertically immersed in the γ-aminopropyltrimethoxysilane ethanol solution of 1wt% and activate 30min, dry, vertically be immersed in 1h in the cadmium telluride solution of 3-thiohydracrylic acid modification, dry, repeat vertically to be immersed in for 4 times 1h and dry step in the cadmium telluride solution that Thiovanic acid modifies again, obtain the fluorescence membrane sensing composite material of 5 layers of quantum dot.
Embodiment 3
A preparation method for fluorescence membrane sensing composite material, described preparation method comprises the steps:
1. the water-soluble poly phenylethylene micro ball being 240nm by 300 μ L particle diameters joins in 5mL deionized water, ultrasonic vibration 30min, by in the conductive glass partial insertion water-soluble poly phenylethylene micro ball aqueous solution, 55 DEG C of reaction 12h, obtain the water-soluble poly phenylethylene micro ball photon crystal film being covered in conductive glass surface;
2. 100mg Cadmium chloride fine powder is dissolved in 100mL high purity water, add the 2mol/L sodium hydroxide solution of 25.0mg2-thiohydracrylic acid, 5mL successively, letting nitrogen in and deoxidizing 30min, add 1mL quantum dot precursor liquid, 80 DEG C of hydro-thermal reaction 7h, obtain the cadmium telluride solution that 2 mercaptopropionic acid is modified; By step 1. products obtained therefrom be vertically immersed in the N-β-aminoethyl-γ-aminopropyltrimethoxysilane ethanol solution of 1wt% and activate 30min, dry, vertically be immersed in 1h in the cadmium telluride solution of 2 mercaptopropionic acid modification, dry, repeat vertically to be immersed in for 4 times 1h and dry step in the cadmium telluride solution that 2 mercaptopropionic acid modifies again, obtain the fluorescence membrane sensing composite material of 5 layers of quantum dot.
Embodiment 4
A preparation method for fluorescence membrane sensing composite material, described preparation method comprises the steps:
1. the water-soluble poly phenylethylene micro ball being 240nm by 300 μ L particle diameters joins in 5mL deionized water, ultrasonic vibration 30min, conductive glass vertical component is inserted in the water-soluble poly phenylethylene micro ball aqueous solution, 55 DEG C of reaction 12h, obtain the water-soluble poly phenylethylene micro ball photon crystal film being covered in conductive glass surface;
2. 100mg Cadmium chloride fine powder is dissolved in 100mL high purity water, add the 2mol/L sodium hydroxide solution of 25.0mg3-thiohydracrylic acid, 5mL successively, letting nitrogen in and deoxidizing 30min, add 1mL quantum dot precursor liquid, 80 DEG C of hydro-thermal reaction 9h, obtain the cadmium telluride solution that 3-thiohydracrylic acid is modified; By step 1. products obtained therefrom be vertically immersed in the β-Trimethoxy silane base-ethylpyridine ethanol solution of 1wt% and activate 30min, dry, vertically be immersed in 1h in the cadmium telluride solution of 3-thiohydracrylic acid modification, dry, repeat vertically to be immersed in for 4 times 1h and dry step in the cadmium telluride solution that 3-thiohydracrylic acid modifies again, obtain the fluorescence membrane sensing composite material of 5 layers of quantum dot.
Comparative example 1
A kind of preparation method of existing fluorescence membrane sensing composite material, described preparation method is for be dissolved in 100mL high purity water by 100mg Cadmium chloride fine powder, add the 2mol/L sodium hydroxide solution of 21.7mg Thiovanic acid, 5mL successively, letting nitrogen in and deoxidizing 30min, add 1mL quantum dot precursor liquid, 80 DEG C of hydro-thermal reaction 12h, obtain the cadmium telluride solution that Thiovanic acid is modified; Conductive glass is vertically immersed in 1h in the cadmium telluride solution that Thiovanic acid modifies, dry, then repeat vertically to be immersed in for 4 times 1h and dry step in cadmium telluride solution that Thiovanic acid modifies, obtain the existing fluorescence membrane sensing composite material of 5 layers of quantum dot.
Application examples 1
Configuration concentration is 1000 μ g/LNa respectively
+, 1000 μ g/LK
+, 1000 μ g/LCa
2+, 1000 μ g/LZn
2+, 1000 μ g/LNi
2+, 1000 μ g/LCo
2+, 1000 μ g/LMg
2+, 500 μ g/LFe
3+, 500 μ g/LHg
+, 500 μ g/LAg
+, 50 μ g/LCu
2+solution, fluorescence membrane sensing composite material embodiment 1 obtained is immersed in high purity water, hatching 15min, dry, measures its fluorescence spectrum; Fluorescence membrane sensing composite material embodiment 1 obtained is immersed in the solution of above-mentioned configuration respectively, hatching 15min, dry, measures its fluorescence spectrum; The results are shown in accompanying drawing 2.
Conclusion: Na
+, K
+, Ca
2+, Zn
2+, Ni
2+, Co
2+, Mg
2+ion pair measurement result does not almost affect, Fe
3+, Hg
+, Ag
+ion pair measurement result has certain influence, Cu
2+the impact of this system fluorescence intensity of ion pair is apparently higher than other ions, and its reason is that different metal ions has different binding abilities from quantum dot surface, Cu
2+the reactive force of ion and quantum dot surface is strong, and quenching of fluorescence degree is large, therefore, to Cu
2+the selectivity of ion is good.
Application examples 2
After being dissolved with concentrated nitric acid by copper powder, then be diluted to 1% dust technology the Cu that concentration is 0.2 μ g/L, 0.4 μ g/L, 0.6 μ g/L, 0.8 μ g/L, 1.0 μ g/L
2+solution, is immersed in the solution of above-mentioned configuration by the fluorescence membrane sensing composite material that embodiment 1 and comparative example 1 obtain respectively, hatching 15min, dry, measures its fluorescence spectrum, the results are shown in accompanying drawing 3 ~ 6.
Conclusion:
A, obtained by Fig. 3, the fluorescence membrane sensing composite material obtained by embodiment 1 detects 0 μm of ol/LCu
2+fluorescence intensity be 800a.u., along with Cu
2+the increase of concentration, the fluorescence intensity of whole system reduces, and is regular reduction, and the position of emission peak also offsets simultaneously;
B, obtained by Fig. 4, the linear relationship equation that the fluorescence membrane sensing composite material obtained by embodiment 1 detects is Y=-0.554+13.497*X, and relation conefficient is 0.961, and calculating minimum detectability is 0.019 μm of ol/L;
C, to be obtained by Fig. 5, detect 0 μm of ol/LCu with the existing fluorescence membrane sensing composite material that comparative example 1 obtains
2+fluorescence intensity be 40a.u., along with Cu
2+the increase of concentration, the fluorescence intensity of whole system reduces, and is irregular reduction, 0.2 μm of ol/LCu
2+fluorescence intensity and 0 μm of ol/LCu
2+the fluorescence intensity ratio range of decrease comparatively large, 0.4 ~ 1.0 μm of ol/LCu
2+fluorescence intensity and 0.2 μm of ol/LCu
2+the fluorescence intensity ratio range of decrease less;
D, obtained by Fig. 6, be Y=1.155+11.302*X with the linear relationship equation that the existing fluorescence membrane sensing composite material that comparative example 1 obtains detects, relation conefficient is 0.974, and calculating minimum detectability is 0.04 μm of ol/L.
E, in sum, the fluorescence membrane sensing composite material that the present invention obtains and existing fluorescence membrane sensing composite material are than detecting Cu
2+fluorescence intensity increase, minimum detectability is also lower.
Application examples 3
The existing fluorescence membrane sensing composite material that fluorescence membrane sensing composite material embodiment 1 ~ 4 obtained and comparative example 1 obtain is duplicate detection 0.6 μ g/LCu respectively
2+solution.
Conclusion: the fluorescence membrane sensing composite material that embodiment 1 ~ 4 obtains uses 10 times, and fluorescence intensity still can return to original more than 95%, and does not occur obscission; And the existing fluorescence membrane sensing composite material that comparative example 1 obtains uses 5 times, fluorescence intensity drops to original 92%, uses 6 times, fluorescence intensity drops to original less than 90%, and starts to occur obscission, uses 10 times, there is severe detachment phenomenon, can not continue to use.
Claims (10)
1. a fluorescence membrane sensing composite material, is characterized in that: described material comprises conductive glass, photonic crystal, quantum dot; Described photonic crystal is covered on conductive glass surface and forms photon crystal film, described quantum dot photon crystal film on the surface self-assembly form quantum dot film, the emission peak of described quantum dot is within the scope of the forbidden photon band of photonic crystal.
2. material according to claim 1, it is characterized in that: described photonic crystal is by least one in the photonic crystal of silicon dioxide microsphere, polystyrene microsphere, polyethylene microballoon, polypropylene microballoon, methyl methacrylate microballoon, polyacrylonitrile microballoon, poly-(styrene methyl methacrylate-vinylformic acid) microballoon self-assembly, and the microspherulite diameter that described self-assembly forms photonic crystal is 100 ~ 500nm.
3. material according to claim 1, is characterized in that: described quantum dot is formed by cadmium telluride, Cadmium Sulfide, cadmium selenide, zinc sulphide, zinc selenide or zinc telluridse self-assembly.
4. material according to claim 1, is characterized in that: described quantum dot is the quantum dot that mercaptan carboxylic acid modifies.
5. material according to claim 4, is characterized in that: described mercaptan carboxylic acid is Thiovanic acid, 2 mercaptopropionic acid or 3-thiohydracrylic acid.
6. the preparation method of fluorescence membrane sensing composite material described in claim 1, is characterized in that: described preparation method comprises the steps:
1. insert conductive glass vertical component for the preparation of in the microspheres solution of photonic crystal, 45 ~ 65 DEG C of reaction 10 ~ 20h, obtain the photon crystal film being covered in conductive glass surface;
2. by step 1. products obtained therefrom be vertically immersed in silane coupler solution, dry, be more vertically immersed in water-soluble quantum dot that mercaptan carboxylic acid modifies, dry, obtain fluorescence membrane sensing composite material;
Or by step 1. products obtained therefrom be vertically immersed in silane coupler solution, dry, more repeatedly repeated vertical is immersed in step in the water-soluble quantum dot that mercaptan carboxylic acid modifies and dry, obtains fluorescence membrane sensing composite material.
7. preparation method according to claim 6, is characterized in that: described silane coupling agent is have amino silane coupling agent.
8. preparation method according to claim 7, is characterized in that: described silane coupling agent is at least one in 3-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane and N-β-aminoethyl-γ-aminopropyltrimethoxysilane.
9. preparation method according to claim 6, is characterized in that: described silane coupler solution is 0.5 ~ 2wt% silane coupling agent ethanol solution.
10. the application of fluorescence membrane sensing composite material described in claim 1 on detection metal ion in solution content.
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| CN106186720B (en) * | 2016-07-19 | 2018-12-18 | 湖北大学 | Fluorescent photon crystal film and preparation method thereof |
| CN106947485A (en) * | 2017-03-16 | 2017-07-14 | 电子科技大学 | A kind of synthetic method of quantum dot photonic crystal laminated film |
| CN108099433A (en) * | 2017-12-19 | 2018-06-01 | 苏州中科纳福材料科技有限公司 | The preparation method of counter opal structure anti-counterfeiting transfer printing film |
| CN108465465A (en) * | 2018-04-04 | 2018-08-31 | 广东工业大学 | A kind of semiconductive thin film and preparation method thereof |
| CN108426865A (en) * | 2018-04-11 | 2018-08-21 | 济南大学 | A kind of preparation method and application of surface bond single fluorescent molecular gel glass |
| CN110865074A (en) * | 2019-11-21 | 2020-03-06 | 陕西科技大学 | Photonic crystal heavy metal sensor with immobilized enzyme and preparation method thereof |
| CN113638027A (en) * | 2021-08-04 | 2021-11-12 | 上海应用技术大学 | Preparation method of dual-mode display photonic crystal/perovskite thin film |
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