The method of inorganic perovskite quantum dot probe and preparation method with mercury ion is detectedTechnical field
The present invention relates to field of chemical detection, more particularly to a kind of inorganic perovskite quantum dot probe and preparation method and inspectionThe method for surveying dimercurion concentration.
Background technology
In recent years, inorganic perovskite quanta point material became the newcomer in " quantum dot family ", not only because its have it is glimmeringLight wavelength of transmitted light is narrow, glow color can reconcile the prominent physical and chemical performance such as quantum yield height, and its biochemicalCan also there is unrivaled characteristic：Such as good bio-compatibility, low cytotoxicity.These superior properties cause inorganic calciumTitanium ore quantum dot probe has wide application prospect in the fields such as biochemical and optical analysiss detection.
Dimercurion is the environmental poisonous substance of a kind of serious harm human body and animal health, the chlor-alkali work with hydrargyrum as raw materialIn industry, electronics industry, plastics industry, measurement instrument industry and mercurous pesticide industry production process produce waste water containing dimercurion,Waste gas and waste residue may affect to be up to decades by enrichment on the generation mercury pollution of environment on this area.It gives people body bandThe disease come is potentially included：There is not independently shake, irritability, stutter, timid, anxiety, uneasiness, unstable, emotional, think of in extremityNot want to concentrate, hypomnesis, the symptom such as depression.At present in environment the assay method of dimercurion mainly using etc. fromDaughter atom emission spectrometry, mass spectrography or electrochemical process etc..But the instrument of the needs costliness that these methods have, what is had is not suitable forField assay is done, some method sensitivity, selectivity can not meet detection and require.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of inorganic perovskite quantum dot probe andMethod of the preparation method with dimercurion concentration is detected, it is intended to solve the instrument of the needs costliness that existing method has, have notField assay is suitably done, some method sensitivity, selectivity can not meet the problem that detection is required.
Technical scheme is as follows：
A kind of preparation method of inorganic perovskite quantum dot probe, wherein, including：
Step A, the halogenide of the halogenide of IA races element and lead is mixed, be then ground, the powder being uniformly mixedEnd；
Step B, powder is dissolved in polar solvent under stirring；
Step C, continuation add two or more surface ligand solution under above-mentioned stirring；
Step D, under static condition, add toluene to system be in hypersaturated state, then stand certain hour separate out crystal after,Again Jing is filtered, and obtains inorganic perovskite quantum dot crystal；
Step E, the inorganic perovskite quantum dot crystal for preparing is dissolved in non-polar solven, obtains inorganic perovskite quantum dotProbe.
The preparation method of described inorganic perovskite quantum dot probe, wherein, in step A, IA races element isOne kind in lithium, sodium, potassium, rubidium, caesium；The halogenide of IA races element and the halogenide mixing mol ratio of lead are 1:1~1:10.
The preparation method of described inorganic perovskite quantum dot probe, wherein, in step B, the polar solvent isN, N- dimethyl sulfoxide, N,N-dimethylformamide, glacial acetic acid, methanol, ethanol, ethylene glycol, isopropanol, 2- isopropanols, aniline,Acetonitrile, acetone, pyridine, dioxane, tetrahydrofuran, butyl acetate, valerone, double ethylene glycol bisthioglycolate ethylethers,One or more in 3,3- dimethyl-2-butanones, quinoline, hexamethyl phosphoramide；The volume of the polar solvent is 10 ~ 500ml。
The preparation method of described inorganic perovskite quantum dot probe, wherein, in step C, the surface ligand is moltenLiquid be oleyl amine, Oleic acid, 1- 18-amine., tri octyl phosphine, tributylphosphine, trioctyl phosphine oxide, n- dodecyl mereaptan, dihydrolipoic acid,Dithiothreitol, DTT, Polyethylene Glycol dihydrolipoic acid ester, polymethylacrylic acid-N, N- dimethylaminoethyls, sodium citrate, gelatin,One kind in Polyetherimide, polyvinylpyrrolidone, polyvinyl alcohol；The amount that the surface ligand solution is added is polar solventThe 1 ~ 20% of volume.
The preparation method of described inorganic perovskite quantum dot probe, wherein, in step D, what the toluene was addedMeasure as 100 ~ 1000 ml；Time of repose is 5 ~ 30 minutes.
The preparation method of described inorganic perovskite quantum dot probe, wherein, in step E, the non-polar solvenFor benzene, carbon tetrachloride, normal hexane, isobutyltrimethylmethane., toluene, dichloromethane, diphenyl ether, chloroform, dichloroethanes, Carbon bisulfide, hexamethyleneOne or more in alkane, hexane, petroleum ether.
The preparation method of described inorganic perovskite quantum dot probe, wherein, in step E, the inorganic perovskiteThe mass range of quantum dot crystal is 0.05 ~ 1mg, and the volume of non-polar solven is 10 ~ 100 ml.
A kind of inorganic perovskite quantum dot probe, wherein, using as above arbitrary described inorganic perovskite quantum dot probePreparation method be prepared from.
A kind of method for detecting dimercurion concentration using inorganic perovskite quantum dot probe as above, wherein,Including：
The linear relationship of step S, the fluorescence intensity for setting up inorganic perovskite quantum dot probe solution and dimercurion concentration, leads toCross and calculate linear relationship equation；
Step T, in inorganic perovskite quantum dot probe solution, add containing dimercurion solution to be measured, detection described twoThe fluorescence intensity of valency mercury ion, the linear relationship equation drawn according to step S determines the dense of dimercurion in solution to be measuredDegree.
The method that described inorganic perovskite quantum dot probe detects dimercurion concentration, wherein, step S is concreteIncluding：The inorganic perovskite quantum dot probe solution that six groups of concentration is 0.005 mg/ml is prepared, a certain amount of dimercurion is addedSolution, makes the dimercurion ultimate density in inorganic perovskite quantum dot probe solution be respectively 0,8 × 10-6、2×10-5、8×10-5、2×10-4、3×10-4Mol/L, surveys respectively the fluorescence intensity of above-mentioned six groups of solution, by being calculated linear relationship sideFormula y=1.72711 × 10-6+ 1962.14x, wherein, x is the concentration of dimercurion, and y is the fluorescence intensity of solution.
Beneficial effect：The present invention is by by the halogenide mixed grinding of the halogenide of IA races element and lead, being then dissolved in poleProperty solvent in, and add surface ligand solution, add toluene until supersaturation, stand the crystal for separating out be re-dissolved in it is nonpolar moltenIn agent, inorganic perovskite quantum dot probe is prepared, the probe can realize quick, highly sensitive knowledge to dimercurionNot.
Description of the drawings
Fig. 1 is the inorganic perovskite quantum dot probe solution in the embodiment of the present invention 1 under different dimercurion concentrationThe relation schematic diagram of fluorescence intensity and fluorescence exciting wavelength.
Fig. 2 is that the fluorescence intensity of inorganic perovskite quantum dot probe solution in the embodiment of the present invention 1 is dense with dimercurionThe linear relationship schematic diagram of degree.
Specific embodiment
The present invention provides the side of a kind of inorganic perovskite quantum dot probe and preparation method and detection dimercurion concentrationMethod, to make the purpose of the present invention, technical scheme and effect clearer, clear and definite, below the present invention is described in more detail.ShouldWork as understanding, specific embodiment described herein only to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of preparation method preferred embodiment of inorganic perovskite quantum dot probe, wherein, including：
Step A, the halogenide of the halogenide of IA races element and lead is mixed, be then ground, the powder being uniformly mixedEnd；
Step A is specifically, by the halogenide of the halogenide of IA races element and lead with certain molar ratio in lapping device（Such as mortar）Middle mixing, is then ground, the pressed powder being uniformly mixed.Wherein, IA races element can beOne kind in lithium, sodium, potassium, rubidium, caesium, preferred IA races element is lithium；The halogen can be the one kind in chlorine, bromine, iodine, excellentThe halogen of choosing is bromine；The halogenide of IA races element and the halogenide mixing mol ratio of lead can be 1:1~1:10, preferablyMol ratio is 1:1.
Step B, powder is dissolved in polar solvent under stirring；
Step B is specifically, by the powder for mixing in stirring（Such as magnetic agitation）Under be dissolved in the polarity of certain volumeIn solvent.Wherein, the polar solvent can be N, N- dimethyl sulfoxide, DMF, glacial acetic acid, methanol, secondAlcohol, ethylene glycol, isopropanol, 2- isopropanols, aniline, acetonitrile, acetone, pyridine, dioxane, tetrahydrofuran, butyl acetate, 2,6-One kind in valerone, double ethylene glycol bisthioglycolate ethylethers, 3,3- dimethyl-2-butanones, quinoline, hexamethyl phosphoramide etc.Or it is various, preferred polar solvent be N, N- dimethyl sulfoxide；The volume of the polar solvent be 10 ~ 500 ml, preferred poleProperty solvent volume be 50 ml.Mixing time is 10 ~ 60 minutes, and preferred mixing time is 20 minutes；Mixing speed is 50 ~ 500Rpm, preferred mixing speed is 150 rpm.
Step C, continuation add surface ligand solution under above-mentioned stirring；
Step C is specifically, continue under above-mentioned stirring, to add a certain amount of surface to match somebody with somebody with given pace syringe pumpLiquid solution.Wherein, the surface ligand solution can be oleyl amine, Oleic acid, 1- 18-amine., tri octyl phosphine, tributylphosphine, trioctylphosphinePhosphine oxide, n- dodecyl mereaptan, dihydrolipoic acid, dithiothreitol, DTT, Polyethylene Glycol dihydrolipoic acid ester, polymethylacrylic acid-N,Two kinds or two in N- dimethylaminoethyls, sodium citrate, gelatin, Polyetherimide, polyvinylpyrrolidone, polyvinyl alcohol etc.More than kind, preferred surface ligand solution is oleyl amine and 1- 18-amine., and the amount that oleyl amine is added is the 5 ~ 20% of polar solvent volume,It is preferred that the 20% of polar solvent volume, drop rate scope is 0.1 ~ 0.5 ml/min, preferably 0.25 ml/min；1- 18-amine. dripsThe volume of addition is the 1 ~ 10%, the 4% of preferred polar solvent volume of polar solvent volume, and drop rate scope is 0.1 ~ 0.8Ml/min, preferably 0.1 ml/min.
Step D, under static condition, add toluene to system to be in hypersaturated state, then stand certain hour separate out it is brilliantAfter body, then Jing is filtered, and obtains inorganic perovskite quantum dot crystal.
Step D adds the toluene of certain volume specifically, under static condition, makes system in hypersaturated state,Certain hour is stood again separates out crystal, then Jing is filtered, and obtains inorganic perovskite quantum dot crystal.Wherein, the toluene is addedMeasure as 100 ~ 1000 ml, preferably 250 ml；Time of repose is 5 ~ 30 minutes, preferably 10 minutes.
Step E, above-mentioned inorganic perovskite quantum dot crystal is dissolved in non-polar solven, obtains inorganic perovskite quantum dotProbe.
Step E by a certain amount of inorganic perovskite quantum dot crystal for preparing specifically, be dissolved in certain volumeIn non-polar solven, inorganic perovskite quantum dot probe is obtained；Wherein, the non-polar solven can be benzene, carbon tetrachloride, justHexane, isobutyltrimethylmethane., toluene, dichloromethane, diphenyl ether, chloroform, dichloroethanes, Carbon bisulfide, hexamethylene, hexane, petroleum ether etc.In one or more, preferred non-polar solven be normal hexane；The mass range of the inorganic perovskite quantum dot crystal is0.05 ~ 1mg, preferred 0.1mg, the volume of non-polar solven is 10 ~ 100 ml, preferred 20ml.Based on said method, the present invention is alsoA kind of inorganic perovskite quantum dot probe is provided, it adopts the preparation side of as above arbitrary described inorganic perovskite quantum dot probeMethod is prepared from.
The present invention also provides one kind and detects dimercurion concentration using inorganic perovskite quantum dot probe as aboveMethod, wherein, including：
The linear relationship of step S, the fluorescence intensity for setting up inorganic perovskite quantum dot probe solution and dimercurion concentration, leads toCross and calculate linear relationship equation；
Step S is added specifically, prepare the inorganic perovskite quantum dot probe solution that six groups of concentration are 0.005 mg/mlA certain amount of dimercurion solution, make the dimercurion ultimate density in inorganic perovskite quantum dot probe solution be respectively 0,8×10-6、2×10-5、8×10-5、2×10-4、3×10-4Mol/L, surveys respectively the fluorescence intensity of above-mentioned six groups of solution, by meterCalculation obtains linear relationship equation y=1.72711 × 10-6+ 1962.14x, wherein, x is dimercurion concentration, and y is solutionFluorescence intensity.Wherein fluorescence exciting wavelength scope is 300 ~ 380 nm, and preferably 350 nm are excited.
Step T, in inorganic perovskite quantum dot probe solution, add containing dimercurion solution to be measured, detect instituteThe fluorescence intensity of dimercurion is stated, the linear relationship equation drawn according to step S determines dimercurion in solution to be measuredConcentration.
Step T is specifically, choose that to measure its fluorescence by above-mentioned steps S containing any concentration dimercurion solution strongDegree, brings above-mentioned gained linear relationship equation into, you can obtain dimercurion concentration.
Loaded down with trivial details with existing plasma atomic emission spectrometry, mass spectrography and electrochemical process these method pretreatment process,Analysis detection time is long, and detection sensitivity is not high to be compared, and said method of the present invention is easily operated, and repeatability is high, and detection is fastSpeed and sensitivity height, can realize quick, high sensitivity identification, test limit as little as 1.72711 × 10 to dimercurion-6 mol/L。
Below by embodiment, the present invention is described in detail.
Embodiment 1
The preparation of red inorganic perovskite quantum dot probe：By the halogenide of the halogenide of IA races element and lead with certain moleRatio mixes in mortar, and wherein IA races element is potassium element；Halogen is bromo element；Potassium bromide mixes mol ratio with lead bromideFor 1:1.
The pressed powder for mixing is dissolved in the polar solvent of certain volume in magnetic agitation state, wherein polar solventFor N, N- dimethyl sulfoxide；Polar solvent volume is 50 ml, and the magnetic agitation time is 20 minutes, and magnetic stirring speed is 150rpm。
Under above-mentioned magnetic agitation, a certain amount of two kinds of surface ligand solution is added with syringe pump with given pace, whereinSurface ligand solution is oleyl amine and 1- 18-amine., and oleyl amine Deca volume is the 20% of polar solvent volume, and drop rate scope is0.25 ml/min.1- 18-amine. Deca volume is the 4% of polar solvent volume, and drop rate scope is 0.1 ml/min.
Under static condition, certain volume toluene is added, make solution in hypersaturated state, stood certain hour and obtain nothingMachine perovskite quantum dot crystal.Volume of toluene is 250 ml, and time of repose is 10 minutes.
Above-mentioned a certain amount of inorganic perovskite quantum dot crystal is dissolved in a certain amount of non-polar solven, inorganic perovskite is obtainedQuantum dot probe.Wherein non-polar solven is normal hexane.Inorganic perovskite quantum dot crystal mass be 0.1 mg, normal hexane volumeFor 20 ml.
Six groups are prepared on the premise of keeping inorganic perovskite quantum dot probe solution concentration to be 0.005 mg/ml constant,A certain amount of dimercurion solution is added, the dimercurion ultimate density in inorganic perovskite quantum dot probe solution is distinguishedFor 0,8 × 10-6、2×10-5、8×10-5、2×10-4、3×10-4Mol/L, surveys above-mentioned six groups of standard solution fluorescence intensities（a-f）, as shown in figure 1, by being calculated linear relationship equation y=1.72711 × 10-6+ 1962.14x, as shown in Figure 2.ItsMiddle fluorescence exciting wavelength scope is excited for 350 nm.
Selection measures its fluorescence intensity containing dimercurion solution by above-mentioned 6th one step process, brings above-mentioned gained into linearGoverning equation, you can obtain dimercurion concentration.
Embodiment 2
（1）The preparation of blue inorganic perovskite quantum dot probe：By the halogenide of the halogenide of IA races element and lead necessarily rubbingYou mix ratio in mortar, and wherein IA races element is potassium element；Halogen is bromo element；Potassium bromide mixes mole with lead bromideThan for 1:1.2.
（2）The pressed powder for mixing is dissolved in the polar solvent of certain volume in magnetic agitation state, wherein polaritySolvent is N, N- dimethyl sulfoxide；Solvent volume is 50 ml, and the magnetic agitation time is 20 minutes, and magnetic stirring speed is 150rpm。
（3）Under above-mentioned magnetic agitation, a certain amount of two or more surface is added with syringe pump with given paceLigand solution, wherein surface ligand solution include oleyl amine and 1- 18-amine..Oleyl amine Deca volume is the 20% of polar solvent volume,Drop rate is 0.35 ml/min.1- 18-amine. Deca volume is the 4% of polar solvent volume, and drop rate is 0.15 ml/min。
（4）Under static condition, certain volume toluene is added, make solution in hypersaturated state, stood certain hour and obtainTo inorganic perovskite quantum dot crystal.Volume of toluene is 250 ml, and time of repose is 10 minutes.
（5）Above-mentioned a certain amount of inorganic perovskite quantum dot crystal is dissolved in a certain amount of non-polar solven, inorganic calcium is obtainedTitanium ore quantum dot probe.Wherein non-polar solven is normal hexane.Inorganic perovskite quantum dot crystal mass be 0.1 mg, normal hexaneVolume is 20 ml.
（6）It is the constant premises of 0.005 mg/ml that six groups are prepared inorganic perovskite quantum dot probe solution concentration is keptUnder, add a certain amount of dimercurion solution to make the dimercurion ultimate density in inorganic perovskite quantum dot probe solution pointWei 0,8 × 10-6、2×10-5、8×10-5、2×10-4、3×10-4Mol/L, surveys above-mentioned six groups of standard solution fluorescence intensities, leads toCross and be calculated linear relationship equation y=1.72711 × 10-6+1962.14x.Wherein fluorescence exciting wavelength scope is 350 nmExcited.
（7）Selection measures its fluorescence intensity containing dimercurion solution by above-mentioned 6th one step process, brings above-mentioned gained intoLinear relationship equation, you can obtain dimercurion concentration.
Embodiment 3
（1）The preparation of green phosphor perovskite quantum dot probe：By the halogenide of the halogenide of IA races element and lead necessarily rubbingYou mix ratio in mortar, and wherein IA races element is sodium element；Halogen is chlorine element；Sodium Chloride mixes mole with lead chlorideThan for 1:10.
（2）The pressed powder for mixing is dissolved in the polar solvent of certain volume in magnetic agitation state, wherein polaritySolvent is hexamethyl phosphoramide；Solvent volume is 50 0ml, and the magnetic agitation time is 60 minutes, and magnetic stirring speed is 50rpm.
（3）Under above-mentioned magnetic agitation, a certain amount of two or more surface is added with syringe pump with given paceLigand solution, wherein surface ligand solution include Oleic acid and polyvinyl alcohol.Oleic acid Deca volume is the 5% of polar solvent volume, dropRate of acceleration is 0.1ml/min.Polyvinyl alcohol Deca volume is the 10% of polar solvent volume, and drop rate is 0.8 ml/min.
（4）Under static condition, certain volume toluene is added, make solution in hypersaturated state, stood certain hour and obtainTo inorganic perovskite quantum dot crystal.Volume of toluene is 1000ml, and time of repose is 30 minutes.
（5）Above-mentioned a certain amount of inorganic perovskite quantum dot crystal is dissolved in a certain amount of non-polar solven, inorganic calcium is obtainedTitanium ore quantum dot probe.Wherein non-polar solven is benzene.Inorganic perovskite quantum dot crystal mass is 1mg, and benzene volume is 100ml。
（6）It is the constant premises of 0.005 mg/ml that six groups are prepared inorganic perovskite quantum dot probe solution concentration is keptUnder, add a certain amount of dimercurion solution to make the dimercurion ultimate density in inorganic perovskite quantum dot probe solution pointWei 0,8 × 10-6、2×10-5、8×10-5、2×10-4、3×10-4Mol/L, surveys above-mentioned six groups of standard solution fluorescence intensity (a-F), by being calculated linear relationship equation y=1.72711 × 10-6+1962.14x.Wherein fluorescence exciting wavelength is 380nm。
（7）Selection measures its fluorescence intensity containing dimercurion solution by above-mentioned 6th one step process, brings above-mentioned gained intoLinear relationship equation, you can obtain dimercurion concentration.
In sum, a kind of inorganic perovskite quantum dot probe of the invention and preparation method are dense with detection dimercurionThe method of degree, loaded down with trivial details with existing plasma atomic emission spectrometry, mass spectrography and electrochemical process these method pretreatment process,Analysis detection time is long, and detection sensitivity is not high to be compared, and said method of the present invention is easily operated, and repeatability is high, and detection is fastSpeed and sensitivity height, can realize quick, high sensitivity identification, test limit as little as 1.72711 × 10 to dimercurion-6 mol/L。
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, and for those of ordinary skills, canTo be improved according to the above description or be converted, all these modifications and variations should all belong to the guarantor of claims of the present inventionShield scope.