CN107271409A - A kind of method that use detects metal ion in solution based on the nanocrystalline metal ion sensor of perovskite - Google Patents
A kind of method that use detects metal ion in solution based on the nanocrystalline metal ion sensor of perovskite Download PDFInfo
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- CN107271409A CN107271409A CN201710203100.8A CN201710203100A CN107271409A CN 107271409 A CN107271409 A CN 107271409A CN 201710203100 A CN201710203100 A CN 201710203100A CN 107271409 A CN107271409 A CN 107271409A
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- perovskite
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- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 19
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 halide ion Chemical group 0.000 claims abstract description 11
- 239000002159 nanocrystal Substances 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 230000008859 change Effects 0.000 claims abstract description 8
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical group [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 3
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000008157 edible vegetable oil Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 3
- 238000013507 mapping Methods 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 238000005424 photoluminescence Methods 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 239000010687 lubricating oil Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 23
- 238000012360 testing method Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 description 14
- 239000002096 quantum dot Substances 0.000 description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- XVBODFCHDIQCGK-KVVVOXFISA-N copper;(z)-octadec-9-enoic acid Chemical compound [Cu].CCCCCCCC\C=C/CCCCCCCC(O)=O XVBODFCHDIQCGK-KVVVOXFISA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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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
-
- 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"
- G01N2021/6432—Quenching
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- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of method that use detects metal ion in solution based on the nanocrystalline metal ion sensor of perovskite.The metal ion sensor of the present invention is nanocrystalline for perovskite, and its crystal structure formula is ABX3Middle A is cesium ion Cs+, B is lead ion Pb2+, X is halide ion Cl‑、Br‑、I‑In one or more, detectable metal ion includes but is not limited to Cu2+、Yb3+Deng metal ion.It will be added to containing the solution for treating measured ion in perovskite nanocrystal solution, the change of the nanocrystalline fluorescence intensity of lower perovskite excited by measuring light, calculate the concentration for obtaining ion to be measured.The transducer sensitivity is high, selectivity strong, low test limit, fast response time, cheap, detection range are wide, test condition is gentle（Room temperature is detected）, easy to operate, high repeatability and other advantages, had a wide range of applications in environment, industry and the metal ion detection field of food.
Description
Technical field
Metal ion in solution is detected based on the nanocrystalline metal ion sensor of perovskite the present invention relates to a kind of use
Method, refer specifically to by metal ion to the nanocrystalline fluorescence of perovskite be quenched or enhancement effect detects metal ion and true
Its fixed concentration.
Background technology
Among metal ion is universally present in biosystem, there is important influence to human health.For example, metal from
Sub- Pb2+、 Hg2+And Cd2+It is not the necessary composition of biological existence, and to the mankind even on low-down concentration level
Health is also harmful；And metal ion such as Fe3+, Cu2+, Mn2+And Zn2+It is then for maintaining health that there is positive effect.Due to
There is highly sensitive metal ion inspection to show for significance of the metal ion in life science and environment science, exploitation
Obtain more and more important, to so far, many ion probes based on organic dyestuff have been developed in people, for detecting life
Or the metal ion in environmental system.
Semiconductor nano (or quantum dot) has many photophysical properties for being better than organic dyestuff, therefore, can be used as
Optical markings in terms of or bio-sensing.Fluorescent type sensor based on organic dyestuff is with itself and higher sensitivity and operation
Simple the characteristics of, is better than other method.However, the shortcoming of organic dyestuff is it is also obvious that such as signal intensity is low, easy photobleaching,
Excitation spectrum is narrow, and emission spectrum is wide, it is difficult to analyze different material simultaneously in same sample.Compared with organic dyestuff, partly lead
Body is nanocrystalline/and the fluorescence of quantum dot can be regulated and controled by size and composition, and wave band, outstanding fluorescence letter are excited with very wide
Number intensity and anti-light bleaching characteristic.Therefore, quantum dot as its high-fluorescence quantum yield of fluorescence probe and stability make its
Service life is also improved while with high sensitivity.Because nanocrystalline optical property is special strongly by its surface
Property, analyte and nanocrystal surface occur interaction and can cause the great variety of its optical property, therefore can widely be used
To detect each metal ion species.In addition, part or acceptor molecule can reach in the secondary modificalion of quantum dot surface and not cause bright
The effect of aobvious fluorescent quenching, it is possible thereby to realize being spatially separating for the centre of luminescence and analyte recognition site.
Due to These characteristics, semiconductor nano/quantum dot is not only only applied to detection small molecule, protein and nucleic acid
Molecule etc., also achieves a series of progress in terms of for detecting metal ion, and such as CdS, ZnS, CdSe, CdTe, PbS receive
Meter Jing/quantum dot be used to detect Fe3+、Cu2+、Pb2+、Hg2+、Zn2+Deng metal ion.Reported semiconductor nano (or amount
Sub- point) detect that the principle and strategy of metal ion include：Metal ion directly contacts with each other effect, right with nanocrystalline/quantum dot
Nanocrystalline/quantum dot surface carry out special chemical ligand modification and metal ion interaction, metal ion directly with nanometer
Crystalline substance/quantum dot noncontact effect fluorescence as caused by energy/electro transfer etc. or electrochemical signals change.Conventional metals ion is examined
Survey mainly passes through atomic absorption spectrography (AAS), inductive coupling plasma mass spectrometry, ion-exchange chromatography, electrochemical process, chemiluminescence, base
In absorption spectrum and colorimetric method of organic dyestuff etc..Although these technology sensitivity are higher, high specificity, exist before sample
Handle complex, instrument it is costly and need professional operate etc. require, metal ion Site Detection application in by
To limitation.Metal ion sensor based on nanocrystalline/quantum dot all has obvious advantage in these areas, but simultaneously, profit
Also there is lot of challenges with nanocrystalline photoluminescent property detection metal ion, one of them is exactly that to need exploitation detection range badly wide,
Test limit is low, sensitivity is high simultaneously material and method；Existing nanocrystalline detection metal ion is typically to be carried out in aqueous phase, and
Lack the metal ion that effective detection organic phase solution is particularly in nonpolar organic solvent.
The content of the invention：
There is provided a kind of cheap, easy to operate, high sensitivity, height for advantage of the invention using nanocrystalline fluoroscopic examination
The method of metal ion in selectivity and the wide detection organic solvent of detection range.Technical scheme is as follows：
The metal ion sensor is by perovskite is nanocrystalline and its surface ligand molecular composition.Perovskite in the present invention is received
Meter Jing, it is the nanocrystalline of perovskite structure to refer in particular to photoluminescence property, material structure, and its crystal structure formula is
ABX3, wherein A is cation caesium (Cs+), B is metal ion Pb2+, X is halide ion Cl-、Br-、I-Or its mixture, including
CsPbCl3、CsPbBr3、CsPbI3、CsPbBrxCl3-x、CsPbIxBr3-x、CsPbIxCl3-x、CsPbIxBryCl3-x-y.The calcium titanium
Ore deposit is nanocrystalline to be less than 20nm at least in a dimension, can include but is not limited to the nanometer of length of side 3-20nm cubic shaped
Crystalline substance, thickness 1-5nm nanocrystalline thin slice, diameter 2-20nm nano wire etc..The nanocrystalline surface modification part, can include
But oleic acid, oleyl amine etc. are not limited to, these surface ligands both play that stable perovskite is nanocrystalline, realize the work of high-fluorescence quantum yield
With causing perovskite is nanocrystalline can preferably be scattered in organic solvent again, including and be not limited to toluene, hexamethylene, dichloromethane
The neat solvents such as alkane, chloroform or its mixed solvent.For detect metal ion perovskite nanocrystal solution concentration for 1.0 ×
10-13To 1.0 × 10-5M。
The present invention is detected to the metal ion in solution in accordance with the following steps：
(1) preparation of perovskite nanocrystalline metal ion transducer：Synthesis perovskite is nanocrystalline, and being made into concentration is
1.0×10-13
To 1.0 × 10-5M dispersion soln；
(2) drafting of metal ion standard detection curve to be measured：Metal ion to be measured is added in nanocrystal solution,
It is to be measured
Concentration of metal ions is 1.0 × 10-11To 1.0 × 10-3The change of nanocrystalline fluorescence intensity is measured in the range of M, with
It is relatively glimmering
Luminous intensity and concentration of metal ions are that standard curve is drawn in coordinate mapping；
(3) metal ion in sample is detected with the nanocrystalline sensor of above-mentioned perovskite：Into perovskite nanocrystal solution
Add
Testing sample solution, detects the intensity of fluorescence signal, and sample is calculated with reference to metal ion standard detection curve to be measured
In it is to be measured
The concentration of metal ion.
The metal ion sensor nanocrystalline based on perovskite of the present invention, with sensitivity is high, test limit is low, response is fast
Degree is fast, selectivity is high, detection range is wide, cheap, gently (room temperature detection), easy to operate, favorable reproducibility etc. are excellent for test condition
Point.Therefore the metal ion sensor of the present invention is applied to the metal ion of industrial chemical, environment and food security aspect
Quick detection.
Brief description of the drawings
Fig. 1 .CsPbBr3The nanocrystalline transmission electron microscope photo of perovskite.
Fig. 2 .CsPbBr3The fluorescence intensity spectrogram of the nanocrystalline detection copper ion of perovskite.
Fig. 3 .CsPbBr3The nanocrystalline detection Cu of perovskite2+Or Yb3+The fluorescence relative intensity standard curve of ion.
Fig. 4 .CsPbBr3Perovskite is nanocrystalline to the selective schematic diagram of different metal ions
Fig. 5 .CsPbBr3Perovskite is nanocrystalline to Cu in edible oil and automobile oil2+Detection.Wherein edible oil A, B
It is three kinds of different commercialization edible oils through the processing of the processes such as decolouring with C；Edible oil D and E are undressed two kinds squeezings
Oil；Edible oil C after fried food；Use front and rear automobile oil.
Fig. 6 .CsPbCl3、CsPbBr3And CsPbI3The nanocrystalline X-ray powder diffraction spectrogram of perovskite.
Fig. 7 (a) CsPbCl3、(b)CsPbCl1.5Br1.5、(c)CsPbBr1.5I3CsPbI (d)3Nanocrystalline detection Cu2+From
The fluorescence relative intensity standard curve of son.
Embodiment
For the present invention is better described, typical but non-limiting embodiment of the invention is as follows.
Embodiment 1
(1)CsPbX3- R (X=Br-, I-, Cl-Or Br-/I-, Cl-/Br-Mixed halogen ion；R is oleic acid and oleyl amine etc.) calcium
The nanocrystalline preparation of titanium ore：Reaction is prepared to carry out in Schlenk line reactors.Weigh 163mg Cs2CO3In 100ml tri-
Neck flask, and 8ml octadecylenes and 0.5ml oleic acid are added thereto, 1h is vacuumized under the conditions of 120 DEG C, magnetic agitation, it is extremely all
Cs2CO3And elaidin reaction, oleic acid caesium presoma is obtained.Added in equipped with thermocouple, the 50ml three-neck flasks of condenser pipe
0.188mmol PbX2(X=Br-, I-, Cl-Or Br-/I-, Cl-/Br-Mixed halogen ion), 5ml octadecylenes, 0.5ml oleic acid and
0.5ml oleyl amines, setting program temperature control, making reaction system, 10min is warming up to 120 DEG C and is kept for 120 DEG C take out true under magnetic stirring
Empty 1h.Make to be warming up to 150 DEG C in 3min under argon gas guard mode afterwards, with syringe by the oleic acid caesium forerunner of foregoing preparation
Liquid solution 0.4ml is rapidly injected, and reaction stops reaction with frozen water cooling immediately after 5 seconds.Mixed liquor after cooling is poured into 10ml
Centrifuge tube, 12000rpm centrifugation 3min, takes lower sediment, is dissolved in hexamethylene, then centrifuges 1min with 3000rpm rotating speed, takes
Layer clear liquid is preserved in cyclohexane solution, obtains uniform solution.
(2) prepared by metal ion standard liquid：Weigh 0.1mmol CuCl2·2H2O, is added dropwise 0.5mL deionized water dissolvings,
0.25mL 0.1M sodium oleate solution is added, ultrasound makes to be sufficiently mixed, centrifuged, remove supernatant liquor, obtained oleic acid
Copper solid is dried in vacuo 5 hours at 80 DEG C, removes moisture removal.Dissolved with 1mL hexamethylenes, obtain the copper oleate that concentration is 0.1M molten
Liquid, it is 0.1 to 1 × 10 to be then diluted to concentration-10M is standby.Other metal ion standard liquid preparation methods ibid, metal from
Son includes but is not limited to Yb3+、Er3+、Ca2+、Au3+、Na+、Mg2+、Al3+、Mn2+、K+、Ni2+、Co2+、 Sn2+、Fe3+、Zn2+、Ag+、
Pb2+、Cd2+Deng.
(3) perovskite nanocrystalline metal ion transducer detects the Specification Curve of Increasing of copper ion：By CsPbBr3It is nanocrystalline
It is made into concentration 1.0 × 10-9M, takes solution 2ml to be placed in cuvette, and its fluorescence intensity is measured with XRF.Will be different in (2)
The copper ion standard liquid of concentration is added in perovskite nanocrystal solution so that copper ion concentration is 2.0 × 10-12To 2.0 ×
10-4M is adjustable, measures fluorescence intensity change, and standard curve is drawn with relative intensity of fluorescence and copper ion concentration mapping.
(4) perovskite nanocrystalline metal ion transducer is to copper ion selective enumeration method：By in (2) method prepare it is identical
The different metal ions standard liquid of concentration is added in (3) in perovskite nanocrystal solution, makes metal ion in solution concentration
For 2.0 × 10-6M, measures fluorescence intensity change.Changed with relative intensity of fluorescence and mapped, it can be seen that there was only copper ion pair
CsPbBr3It is nanocrystalline to have fluorescence quenching, show CsPbBr3The selection that nanocrystalline metal ion transducer is detected to copper ion
Property is fine.
(5) copper ion in solution example to be measured is detected：To CsPbBr3Testing sample solution is added in nanocrystal solution,
Such as edible oil, fluorescence intensity.After being added through the edible oil of the processes such as decolouring processing in perovskite nanocrystal solution, its fluorescence
Intensity is almost unchanged；And undressed squeezing edible oil, fluorescence intensity is had obvious reduction；It is edible after fried food
Oil, its fluorescence intensity is also significantly reduced.With reference to the standard curve in (3), it can calculate and obtain copper ion in above-mentioned each edible oil
Concentration.Its testing result is consistent with the copper ion concentration that Inductively coupled plasma-mass spectrometry is measured.
Embodiment 2
Other conditions are constant in embodiment 1, and solution example to be measured is changed into using the auto lubrication after preceding and use in (5)
Oil, finds, CsPbBr relatively low using content of copper ion in preceding automobile oil3Nanocrystalline fluorescence intensity only has small size decline；And
Content of copper ion is higher in automobile oil after use, to CsPbBr3Nanocrystalline fluorescence has significant quenching effect.It is detected
As a result the copper ion concentration measured with Inductively coupled plasma-mass spectrometry meets preferably.
Embodiment 3
(1) and (2) condition is constant in embodiment 1, and metal ion changes Yb into (3)3+, Yb can be passed through3+Enhancing to fluorescence
Effect is to Yb3+Ion concentration is detected.
Embodiment 4
Be the same as Example 1, other conditions are constant, by CsPbBr3It is nanocrystalline to change CsPbCl into3、CsPbCl1.5Br1.5、
CsPbBr1.5I1.5Or CsPbI3It is nanocrystalline, equally can be to Cu2+Detected Deng metal ion.
CsPbX in the present invention of table 1.3Nanocrystalline and other existing representational nanocrystalline detection Cu2+The contrast of ion, tool
The characteristics of having includes：The lower limit of detection is low, metal ion detection suitable for organic solvent, and it is existing other it is nanocrystalline from
Sub- sensor is used to aqueous phase detection.
Claims (6)
1. a kind of method for detecting metal ion in solution, it is characterised in that become by the fluorescence intensity of metal ion sensor
Change, detect the concentration of metal ion in solution；The metal ion sensor is that oil-soluble perovskite is nanocrystalline, its crystal structure
Formula is ABX3, wherein A is cesium ion Cs+, B is lead ion Pb2+, X is halide ion；The nanocrystal surface is modified with surface and matched somebody with somebody
Body；This is nanocrystalline with photoluminescence property；This is nanocrystalline to be less than 20nm at least in a dimension, and can be scattered in organic
Solvent, methods described comprises the following steps：(1) it is 1.0 × 10 in the nanocrystalline concentration of perovskite-13To 1.0 × 10-5Selected in the range of M
A fixed concentration, metal ion standard liquid to be measured is added in perovskite nanocrystal solution, metal to be measured in resulting solution
The concentration of ion is 1.0 × 10-11To 1.0 × 10-3M is adjustable；(2) change of nanocrystalline fluorescence intensity is measured, it is strong with relative fluorescence
Degree and ion concentration to be measured are that standard curve is drawn in coordinate mapping；(3) treated to being added in the solution of (1) same nanocrystalline concentration
Sample solution is surveyed, the nanocrystalline fluorescence intensity of perovskite is detected, calculating Gold Samples with reference to the standard curve in (2) belongs to the dense of ion
Degree.
2. method according to claim 1, it is characterised in that the halide ion is Cl-、Br-、I-In one or more.
3. method according to claim 1, it is characterised in that the surface ligand is that oil-soluble alkyl carboxylic acid and/or oil are molten
Property kiber alkyl amine, wherein the chemical general formula of alkyl carboxylic acid part be R-COO-, R is alkyl, and the chemistry of kiber alkyl amine part leads to
Formula is R'-NH2, R' is alkyl.
4. method according to claim 1, it is characterised in that the nanometer of the nanocrystalline cubic shaped for length of side 3-20nm
Brilliant or thickness is 1-5nm nanocrystalline thin slice or a diameter of 2-20nm nano wire.
5. the method for claim 1, it is characterised in that the organic solvent is toluene, hexamethylene, n-hexane, dichloromethane, chlorine
Imitative, edible oil, lubricating oil or its mixture.
6. the method for claim 1, it is characterised in that the metal ion is Cu2+、Yb3+。
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