CN110386886A - Quickly, the method for exchange colloidal nanocrystals surface ligand highly effective and versatile - Google Patents
Quickly, the method for exchange colloidal nanocrystals surface ligand highly effective and versatile Download PDFInfo
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- CN110386886A CN110386886A CN201810337966.2A CN201810337966A CN110386886A CN 110386886 A CN110386886 A CN 110386886A CN 201810337966 A CN201810337966 A CN 201810337966A CN 110386886 A CN110386886 A CN 110386886A
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- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
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Abstract
The invention discloses a kind of methods of exchange colloidal nanocrystals surface ligand quickly, highly effective and versatile comprising following steps: the colloidal nanocrystals that hydrophobicity organic ligand is contained on surface are dispersed in organic solvent, solution is obtained；Ligand exchange reagent is added into obtained solution, by evenly mixing after, complete colloidal nanocrystals surface ligand exchange.This method has good universality, for a plurality of types of nanocrystals (including different chemical compositions, different surfaces ligand, different-shape nanocrystal) with a plurality of types of ligand exchange reagents (including compounds such as sulfydryl, carboxyl, amino, inorganic salts) can quickly realize exchanging for surface ligand.The ligand exchange reaction can be completed in several minutes, have the characteristics that method is simple, universality is good, atom economy is high, provide desirable route for the extensive use of nanocrystal.
Description
Technical field
The present invention relates to field of nanometer material technology.More particularly, to a kind of quick, exchange colloidal nano highly effective and versatile
The method of plane of crystal ligand.
Background technique
The concept for proposing nanocrystal from Germany scientist professor H.Gleiter the 1980s and artificial preparation for the first time
Since obtaining nanocrystal, nano crystal material receives each because it is with unique architectural characteristic and excellent physico-chemical property
The extensive concern of state scientist and research, especially in fields such as biomedical material, optical material and energy conversions.Therefore,
The preparation and modification of nano material play important impetus to the research of nano material and applications in various fields.
Thermal decomposition method is one of the preparation of colloidal nano material important channel, the especially synthesis of sulfur family nanocrystal
[Chem.Soc.Rev.2011,40,5492-5513；Chem.Mater.2013,25,1351-1362；
Chem.Soc.Rev.2014,43,7520-7535；Chem.Soc.Rev.2014,43,5234-5244；J.Mater.Chem.A
2017,5,21669-21673.].The synthetic strategy of thermolysis process is mainly: with organo-metallic compound and chalcogenide
It for presoma, decomposes in higher boiling organic phase solvent high temperature, nucleation, growth, is prepared that crystallinity is high, size distribution is uniform
Colloidal nanocrystals.Preparation-obtained nanocrystal, surface is usually by the organic ligand of long-chain such as oleic acid, oleyl amine, ten
Tetraalkyl phosphoric acid etc. is stablized, therefore is typically only capable to be dispersed in n-hexane, first by the colloidal nanocrystals that this method is prepared
[Small 2009,5,154-168 in benzene, the lesser organic phase solvent of chloroform isopolarity；Nano Res.2009,2,425-
447；RSC Adv.2014,4,23505-23527.].And in fields such as energy conversions, the nanocrystal of preparation usually requires to turn
It moves on in water phase using [J.Mater.Chem.A 2016,4,2856-2862；Nanoscale 2015,7,5767-5775.].
Therefore, a kind of simple, efficient, universality is good ligand exchange processes, the colloid nanocrystalline body surface that thermal decomposition method is synthesized are developed
The hydrophobic ligand exchange in face becomes hydrophily or the higher short chain organic ligand of polarity, and by nanocrystal by organic phase transfer
Into water phase or alcohols equal solvent, nanocrystal can be greatly facilitated in the application and research in the fields such as energy conversion.
Around the ligand exchange of colloidal nanocrystals, the ligand exchange strategy of existing method is: ligand exchange reagent is molten
Solution is into the solution such as aqueous solution or polar methanol, while it is organic that nanocrystal solution is dissolved into n-hexane or chloroform etc.
In solvent, and two kinds of solvents are mixed, are sufficiently stirred, realizes nanocrystal in two alternate ligand exchange reactions.This method institute
Need the amount of ligand exchange reagent is bigger, the reaction time is long, reaction process is more complicated, part reaction need in a heated condition
It completes, the universality of this method is not good enough yet.Factors above limits popularization and application of the ligand exchange in different systems.
In view of colloidal nanocrystals ligand exchange importance with it is essential, develop one kind and be swift in response, be easy to operate, is general
Adaptive is good, atom economy ligand exchange mode, is an important topic of nanocrystal research and application field.
Summary of the invention
The purpose of the present invention is to provide a kind of sides of exchange colloidal nanocrystals surface ligand quickly, highly effective and versatile
Method, this method is swift in response, is easy to operate, universality is good.
In order to achieve the above objectives, the present invention adopts the following technical solutions:
A method of quick, exchange colloidal nanocrystals surface ligand highly effective and versatile includes the following steps:
The colloidal nanocrystals that hydrophobicity organic ligand is contained on surface are dispersed in organic solvent, solution is obtained；
Ligand exchange reagent is added into obtained solution, by evenly mixing after, complete colloidal nanocrystals surface match
The exchange of body.
Preferably, the mixed method includes stirring or ultrasound, and the mixed time is less than 10min.
Preferably, the method also includes: into solution be added ligand exchange reagent before, further include being added into solution
The step of solid base；Preferably, the solid base in potassium hydroxide, sodium hydroxide, calcium hydroxide and barium hydroxide one
Kind is several；Preferably, the additive amount of the solid base is the 1/2-1/10, more preferably 1/4-1/ of ligand exchange reagent quality
6.The addition of micro solid base can make the nanocrystal after ligand exchange is more stable to be dispersed in corresponding solvent.
Preferably, colloidal nanocrystals include but not in the colloidal nanocrystals that hydrophobicity organic ligand is contained on the surface
It is limited to selected from II-VI group, the colloidal nanocrystals of I-III-VI race.
Preferably, the pattern of the colloidal nanocrystals is zero-dimensional quantum dots, one-dimensional nano line, two-dimensional nano piece, nanometer
One of stick and nano particle.
Preferably, the group of the colloidal nanocrystals becomes one of one-component or various ingredients or a variety of.
Preferably, the nanocrystal of the one-component includes quantum dot, nano wire/nanometer rods, nanometer sheet and nanometer
One of grain.
Preferably, the colloidal nanocrystals of the one-component be selected from CdSe, CdS, CdTe, ZnSe, ZnS, ZnTe,
PbSe、PbS、CuInSe2One or more of.
Preferably, the colloidal nanocrystals of the various ingredients are hud typed or heterojunction type.
Preferably, the colloidal nanocrystals of the various ingredients include quantum dot, nano wire/nanometer rods, in nanometer sheet
It is one or more of.
Preferably, the colloidal nanocrystals of the various ingredients be selected from CdSe/ZnS, CdSe/CdS, CdTe/CdSe,
One or more of ZnSe/CdS, CdS/ZnTe.
Preferably, the hydrophobicity organic ligand is selected from carboxylic acid, amine, phosphoric acid or the phosphino- compound of atomicity containing C >=10；
Preferably, the hydrophobicity organic ligand is being selected from oleic acid, octadecylamine, oleyl amine, myristyl phosphoric acid, octadecyl phosphoric acid, three just
One or more of octyl phosphine.
Preferably, the organic solvent be selected from n-hexane, hexamethylene, benzene, toluene, ethylbenzene, methylene chloride, chloroform,
One or more of carbon tetrachloride.
Preferably, the ligand exchange reagent be selected from the mercaptan carboxylic acids of atomicity≤8 C, mercaptoalcohol, thiol esters, dimercapto,
Carboxylic acid, amino acid, organic heterocyclic molecule or inorganic sulphide；Preferably, the ligand exchange reagent be selected from 3- mercaptopropionic acid,
Thioacetic acid, mercaprol, 3- mercaptobutyric acid ethyl ester, 2,3- dimercaptosuccinic acid, 1,4- dimercapto-DL- threitol, lactic acid,
L-cysteine, pyridine, Na2One or more of S.
Preferably, the mixing carries out at normal temperature.
Preferably, the method also includes following steps: the colloidal nanocrystals that exchange is obtained are dispersed in a solvent,
In, the solvent is selected from polar organic solvent or water.
Preferably, the polar organic solvent is selected from methanol, ethyl alcohol, isopropanol, acetone, ethyl acetate, N, N- dimethyl
One or more of formamide, dimethyl sulfoxide.
In the present invention, the colloidal nanocrystals raw material that hydrophobicity organic ligand is contained on surface is mainly the side for passing through thermal decomposition
Method preparation, as long as surface stablized by the organic ligand of long-chain, can be lesser in n-hexane, toluene, chloroform isopolarity
The nanocrystal of stable dispersion in organic solvent is used equally for this method to realize ligand exchange reaction.The system of part nanocrystal
It is standby to can refer to [Chem.Mater.2013,25,1199-1210；J.Phys.Chem.C 2012,116,25065-25073；
J.Am.Chem.Soc.2003,125,12567-12575；J.Mater.Chem.2003,13,2641-2648；
J.Am.Chem.Soc.2017,139,17305-17308；Nano Lett.2017,17,4165-4171；
J.Am.Chem.Soc.2017,139,10009-10019；Small 2009,5,154-168] etc. document reports synthesis.
Beneficial effects of the present invention are as follows:
In technical solution of the present invention, do not need for ligand exchange reagent to be distributed to water or other highly polar solvents first
In, exactly this improvement achieves unexpected effect, and nanocrystal ligand exchange can be in a small amount of ligand exchange reagent
Under quickly finish.Expansion experiment also turns out this method in colloidal nanocrystals chemical composition, crystal morphology, surface ligand kind
Class and ligand exchange reagent type etc. have good universality.
In addition, technical solution of the present invention can fast implement the exchange of colloidal nanocrystals surface ligand；Reaction condition
Mildly, easy to operate, reproducible；Required ligand exchange reagent is few, and Atom economy is high；It is nanocrystalline before and after ligand exchange reaction
Size, pattern of body etc. will not change；This method universality is strong, which can complete in several minutes,
It is all had in terms of nanocrystal chemical composition, pattern, surface ligand type, reaction dissolvent and ligand exchange wide
General applicability.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows quantum dot/hexane solution before the quantum dot aqueous solution obtained after embodiment 1 is dispersed and ligand exchange
Absorption spectrum.
Fig. 2 shows the nuclear magnetic spectrograms of the quantum dot before and after 1 ligand exchange of embodiment.
Before and after Fig. 3 shows 2 ligand exchange of embodiment, the absorption spectrum of ZnSe quantum dot.
Before and after Fig. 4 shows 3 ligand exchange of embodiment, the Fourier infrared absorption spectrum of CdS nano particle.
Fig. 5 shows the nuclear-magnetism figure of the CdSe quantum dot of the 3- mercaptobutyric acid ethyl ester coordination obtained after 4 ligand exchange of embodiment
Spectrum.
Fig. 6 shows the CdSe quantum dot and bis- mercapto of 2,3- that myristyl phosphoric acid and tri-n-octyl phosphine are coordinated altogether in embodiment 5
Photo before and after base succinic acid ligand exchange.
Fig. 7 is shown in embodiment 6 before and after ligand exchange, the transmission electron microscope photo of CdS nanometer rods.
Fig. 8 shows the absorption spectrum in embodiment 7 before and after CdSe/ZnS core-shell type quantum point ligand exchange.
Fig. 9 shows the absorption spectrum in embodiment 8 before and after ZnSe/CdS hetero-junctions nanometer rods ligand exchange.
Figure 10 show embodiment 9, in 12-14 before and after nanocrystal ligand exchange solution photo.
Figure 11 shows the photo of solution in ligand exchange processes in embodiment 15.
Figure 12 shows the solution thereon in comparative example 1 in conventional ligands exchange process.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
The CdSe quantum dot of oleic acid coordination and the ligand exchange of 3- mercaptopropionic acid, and be distributed in water comprising the steps of:
The CdSe quantum of oleic acid coordination is prepared in [Nano Res.2013,6,652-670] first according to the literature
Point, is distributed in hexane solution after purification；
CdSe quantum dot/the hexane solution for taking 5.0mL to prepare, the NaOH solid and 30 μ L of about 6mg are added into solution
3- mercaptopropionic acid, after stirring 2min at normal temperature, centrifugation；Precipitating n-hexane and water/acetone mixture are respectively washed once, final
To precipitating be dispersed directly into 5.0mL secondary water.
Quantum dot/hexane solution absorption spectrum before the quantum dot aqueous solution and ligand exchange that obtain after dispersion is as schemed
Shown in 1, in the absorption spectrum of two kinds of solvents, is not absorbed at >=600nm, shows there is no scattering phenomenon in solution,
It can be stably dispersed in corresponding solvent before and after quantum dot ligand exchange.On the other hand, before and after ligand exchange, quantum dot
First absorbs peak position (535nm) there is no significantly changing, since the absorption peak position of quantum dot is by the direct of its size
It influences, therefore the size of quantum dot does not change in ligand exchange processes.In addition, the intensity of absorption peak is almost unchanged, also demonstrate,prove
The concentration of quantum dot in ligand exchange processes is illustrated almost without changing, i.e., ligand exchange processes are more complete.
In order to prove that quantum dot surface ligand becomes 3- mercaptopropionic acid by oleic acid, we are to the quantum before and after ligand exchange
Point has carried out nuclear-magnetism characterization, as shown in Figure 2.Before ligand exchange, quantum dot is between chemical shift about 0.5-2.0ppm containing big
The peak of amount, the peak correspond to the hydrogen for long-chain oleic acid ligand in saturated fat area；There is apparent oleic acid at about 5.4ppm simultaneously
Hydrogen on ligand olefinic double bonds, it was demonstrated that the presence of quantum dot surface oleic acid ligand.After ligand exchange, the nuclear-magnetism of quantum dot
Map contains only apparent water peak (4.87ppm) and 2.5ppm two triplets nearby, the two triplets correspond to 3- sulfydryl
Two CH in propionic acid2On hydrogen.The above result shows that the oleic acid ligand on CdSe quantum dot surface is completely by 3- mercaptopropionic acid
Ligand substituting.
Embodiment 2
The ZnSe quantum dot of oleic acid coordination and the ligand exchange of 3- mercaptopropionic acid, and be distributed in water:
With embodiment 1, the difference is that the ZnSe quantum dot that the CdSe quantum dot of oleic acid coordination replaces with oleic acid coordination (is closed
At method with [Nano Res.2013,6,652-670]).Before and after ligand exchange, the absorption spectrum of ZnSe quantum dot such as Fig. 3 institute
Show, absorption spectrum is almost without changing before and after ligand exchange, it was demonstrated that the complete quilt of the oleic acid ligand of ZnSe quantum dot surface
Replaced 3- mercaptopropionic acid, and stable dispersion is in aqueous solution.
Embodiment 3
The CdS nano particle of oleic acid coordination and the ligand exchange of thioacetic acid, and be distributed in water comprising the steps of:
Oleic acid coordination is prepared in [J.Phys.Chem.C 2013,117,11584-11591] first according to the literature
CdS nano particle, be distributed in chloroform soln after purification.
CdS nano particle/the chloroform soln for taking 5.0mL to prepare, the KOH solid and 30 μ of about 6mg are added into solution
L thioacetic acid, after 2min is stirred at room temperature, centrifugation.Precipitating chloroform and water/acetone mixture are respectively washed once, are finally obtained
Precipitating be dispersed directly into 5.0mL secondary water.
Before and after ligand exchange, the Fourier infrared absorption spectral characterization of CdS nano particle is as shown in figure 4, in infrared spectroscopy
Wave number 2900cm-1Locate the stretching vibration peak of the c h bond in corresponding alkyl compound, the intensity at the peak significantly drops after ligand exchange
It is low, it was demonstrated that replaced thioacetic acid ligand of the oleic acid ligand of CdS nano grain surface long-chain by short chain.
Embodiment 4
The CdSe quantum dot of oleic acid coordination and the ligand exchange of 3- mercaptobutyric acid ethyl ester, and be distributed in methanol solution:
With embodiment 1, the difference is that 3- mercaptobutyric acid ethyl ester is used to substitute 3- mercaptopropionic acid as ligand exchange reagent, reaction
It does not need that NaOH is added in the process, the precipitating purified after ligand exchange is dispersed directly into methanol solution.After ligand exchange
The nuclear magnetic spectrum of the CdSe quantum dot of obtained 3- mercaptobutyric acid ethyl ester coordination is as shown in Figure 5.The characteristic peak of methanol is removed in nuclear-magnetism
Outside the chemical shift peak of (3.34ppm) and 3- mercaptobutyric acid ethyl ester, almost without the nuclear-magnetism peak of other compounds, it was demonstrated that quantum dot
The oleic acid ligand on surface is replaced completely by 3- mercaptobutyric acid ethyl ester.
Embodiment 5
The ligand of CdSe quantum dot and 2,3- dimercaptosuccinic acid that myristyl phosphoric acid and tri-n-octyl phosphine are coordinated altogether is handed over
It changes, and is distributed in water, the specific steps of which are as follows:
Myristyl phosphorus is prepared in [J.Phys.Chem.B 2005,109,8538-8542] first according to the literature
The CdSe quantum dot that acid is coordinated altogether with tri-n-octyl phosphine, is distributed in toluene solution after purification.
CdSe quantum dot/the toluene solution for taking 5.0mL to prepare, the NaOH solid and 40 μ L 2 of about 8mg are added into solution,
3- dimercaptosuccinic acid, after 2min is stirred at room temperature, centrifugation.Precipitating toluene and water/acetone mixture are respectively washed once, are finally obtained
Precipitating be dispersed directly into 5.0mL secondary water.Photo before and after ligand exchange is as shown in fig. 6, before ligand exchange, and quantum dot is only
It can be dissolved in the lesser organic solvent toluene of polarity (upper layer), after ligand exchange, obtained 2,3-dimercaptosuccinic acid is coordinated
CdSe quantum dot is completely dissolved in water (lower layer), and toluene layer (upper layer) becomes fully transparent.
Embodiment 6
The CdS nanometer rods and 3- mercaptopropionic acid ligand exchange of octadecyl phosphoric acid coordination, and be distributed in water, it is specific to walk
It is rapid as follows:
The coordination of octadecyl phosphoric acid is prepared referring initially to document report [Langmuir, 2008,24,9043-9049]
CdS nanometer rods, be distributed in dichloromethane solution after purification.
CdS nanometer rods/the dichloromethane solution for taking 2.0mL to prepare, the Ca (OH) of about 6mg is added into solution2Solid and
30 μ L 3- mercaptopropionic acids, after 2min is stirred at room temperature, centrifugation.Precipitating methylene chloride and water/acetone mixture are respectively washed once, most
The precipitating obtained eventually is dispersed directly into 2.0mL secondary water.The CdS nanometer rods of Germicidal efficacy preparation are that the yellow of clear is molten
Liquid, it was demonstrated that the generation of ligand exchange processes.Transmission electron microscope photo before and after ligand exchange is as shown in fig. 7, ligand exchange
The size of nanometer rods illustrates that the structure of nanometer rods during this has obtained good holding there is no variation afterwards.
Embodiment 7
The CdSe/ZnS core-shell quanta dots and 3- mercaptopropionic acid ligand exchange of octadecylamine coordination, and be distributed in water:
Octadecylamine is prepared referring initially to document report [J.Am.Chem.Soc.2010,132,15038-15045] to match
The CdSe/ZnS core-shell quanta dots of position, are distributed in hexane solution after purification.
Nanocrystal is only changed to the CdSe/ZnS nucleocapsid amount of octadecylamine coordination with embodiment 1 by ligand exchange procedures
Sub- point.Before and after ligand exchange, the absorption spectrums of core-shell quanta dots is not as shown in figure 8, core-shell quanta dots are inhaled at >=600nm
It receives, shows that solution does not have scattering phenomenon, i.e., core-shell quanta dots stable dispersion is in aqueous solution after ligand exchange.In addition, ligand is handed over
It changes front and back absorption spectrum to have almost no change, it was demonstrated that no change has taken place for the structure of exchange front and back core-shell quanta dots.
Embodiment 8
The ZnSe/CdS hetero-junctions nanometer rods and 3- mercaptopropionic acid ligand exchange of oleic acid coordination, and be distributed in water:
The ZnSe/CdS hetero-junctions of oleic acid coordination is prepared referring initially to document report [Nat.Commun.2014,5,3642]
Nanometer rods are distributed in dichloromethane solution after purification.
Ligand exchange procedures are with embodiment 6, and ligand exchange front and back, the absorption spectrum of ZnSe/CdS hetero-junctions nanometer rods is as schemed
Shown in 9, the almost unchanged generation for proving ligand exchange processes of absorption curve.
Embodiment 9
The CuInSe of oleyl amine coordination2Nano particle and 3- mercaptopropionic acid ligand exchange, and be distributed in water:
The CuInSe of oleyl amine coordination is prepared referring initially to document report [Chem.Mater.2016,28,1107-1120]2It receives
Meter Jing Ti is distributed in hexane solution after purification.
Nanocrystal is only replaced with CuInSe by CdSe quantum dot with embodiment 1 by ligand exchange procedures2Nanometer
Grain.Before and after ligand exchange, CuInSe2No. 1 sample in the photo such as Figure 10 of nanocrystal.
Embodiment 10
The CdSe quantum dot of oleic acid coordination and the ligand exchange of 3- mercaptobutyric acid ethyl ester, and it is distributed to ethyl acetate solution
In:
With embodiment 4, the difference is that methanol solution is substituted for ethyl acetate solution, it is as a result similar to Example 4.
Embodiment 11
The CdSe quantum dot of oleic acid coordination and the ligand exchange of 3- mercaptopropionic acid, and it is molten to be distributed to n,N-Dimethylformamide
In liquid:
With embodiment 1, the difference is that water is substituted for n,N-Dimethylformamide solution, it is as a result similar to Example 1.
Embodiment 12
The CdS nanometer rods of octadecyl phosphoric acid coordination and the ligand exchange of lactic acid, and be distributed in aqueous solution:
With embodiment 6, ligand exchange reagent is replaced with into lactic acid by 3- mercaptopropionic acid, ligand exchange reaction is in n-hexane
It carries out, being stirred at room temperature after about 10min to react can be completed.Before and after ligand exchange, No. 2 samples in the photo such as Figure 10 of CdS nanometer rods
Product.
Embodiment 13
The CdSe quantum dot of oleic acid coordination and the ligand exchange of L-cysteine, and be distributed in aqueous solution:
With embodiment 1, ligand exchange reagent is replaced with into L-cysteine by 3- mercaptopropionic acid, the ligand exchange processes are only
It stir about 10min need to can be completed at room temperature.Before and after ligand exchange, No. 3 samples in the photo such as Figure 10 of CdSe quantum dot
Product.
Embodiment 14
The ZnSe/CdS hetero-junctions nanometer rods and Na of oleic acid coordination2The ligand exchange of S, and be distributed in aqueous solution:
With embodiment 8, the difference is that ligand exchange reagent is replaced Na by 3- mercaptopropionic acid2S solid, ligand exchange reaction
It is carried out in n-hexane, does not need that alkali is added in ligand exchange processes, stir about 10min reaction at room temperature can be complete
At.Before and after ligand exchange, No. 4 samples in the photo such as Figure 10 of ZnSe/CdS hetero-junctions nanometer rods.
Embodiment 15
3mg NaOH solid and 15 μ L 3- mercaptopropionic acids, room are directly added into 1mL CdSe quantum dot/hexane solution
After temperature stirring 2min, quantum dot ligand exchange situation is as shown in figure 11.Before 3- mercaptopropionic acid is added, CdSe quantum dot/n-hexane
Solution is in Chinese red clear shape；After 3- mercaptopropionic acid is added and stirs 2min, hexane solution is in achromaticity and clarification transparence,
Solution bottom has Chinese red precipitating particle to be formed simultaneously, it was demonstrated that ligand exchange has been fully finished.
Comparative example 1
Referring to conventional ligand exchange processes (Nanoscale 2015,7,5767-5775): by 50 μ L 3- mercaptopropionic acids
Solution is distributed in 1mL water, and the pH=10 of solution is adjusted with NaOH；It is molten that 1mL CdSe quantum dot/n-hexane is added into solution
Liquid, is stirred at room temperature 10h, and the ligand exchange situation of increase at any time, CdSe quantum dot is as shown in figure 12.
When reaction just starts, lower layer's aqueous phase solution is in achromaticity and clarification transparence in system, it was demonstrated that CdSe is free of in water phase
Quantum dot.After reaction carries out about 6h, Chinese red is mutually presented in lower layer's water phase and upper layer n-hexane, it was demonstrated that has had the CdSe of part
Water phase is exchanged to, but n-hexane is mutually still containing the CdSe quantum dot not exchanged largely.When reaction proceeds to 10h, upper layer
The color of hexane solution becomes than thin, but still the Chinese red containing part, illustrates that most CdSe quantum dot exchanges to
Water phase.Namely the exchange that could complete most quantum dot is takeed a long time using the method.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of method of exchange colloidal nanocrystals surface ligand quickly, highly effective and versatile, which is characterized in that including as follows
Step:
The colloidal nanocrystals that hydrophobicity organic ligand is contained on surface are dispersed in organic solvent, solution is obtained；
Ligand exchange reagent is added into obtained solution, by evenly mixing after, complete colloidal nanocrystals surface ligands
Exchange.
2. the method according to claim 1, wherein the mixed method include stirring or ultrasound, mixing
Time is less than 10min.
3. the method according to claim 1, wherein the method also includes: into solution be added ligand hand over
Before changing reagent, further include the steps that solid base is added into solution；Preferably, the solid base is selected from potassium hydroxide, hydroxide
One or more of sodium, calcium hydroxide and barium hydroxide；Preferably, the additive amount of the solid base is ligand exchange reagent matter
The 1/2-1/10 of amount.
4. the method according to claim 1, wherein the colloidal nano of hydrophobicity organic ligand is contained on the surface
Colloidal nanocrystals include but is not limited to be selected from the colloidal nanocrystals of II-VI group, I-III-VI race in crystal；Preferably, institute
The pattern of colloidal nanocrystals is stated as one in zero-dimensional quantum dots, one-dimensional nano line/nanometer rods, two-dimensional nano piece and nano particle
Kind is several；The group of the colloidal nanocrystals becomes one of one-component or various ingredients or a variety of；Preferably, described
The colloidal nanocrystals of one-component are selected from CdSe, CdS, CdTe, ZnSe, ZnS, ZnTe, PbSe, PbS, CuInSe2In one
Kind is several；The colloidal nanocrystals of the various ingredients are hud typed or heterojunction type；It is highly preferred that the various ingredients
Colloidal nanocrystals are selected from one or more of CdSe/ZnS, CdSe/CdS, CdTe/CdSe, ZnSe/CdS, CdS/ZnTe.
5. the method according to claim 1, wherein the hydrophobicity organic ligand is selected from atomicity containing C >=10
Carboxylic acid, amine, phosphoric acid or phosphino- compound；Preferably, the hydrophobicity organic ligand is selected from oleic acid, octadecylamine, oleyl amine, 14
One or more of alkyl phosphoric acid, octadecyl phosphoric acid, tri-n-octyl phosphine.
6. the method according to claim 1, wherein the organic solvent is selected from n-hexane, hexamethylene, benzene, first
One or more of benzene, ethylbenzene, methylene chloride, chloroform, carbon tetrachloride.
7. the method according to claim 1, wherein the ligand exchange reagent is selected from the sulfydryl of atomicity≤8 C
Carboxylic acid, mercaptoalcohol, thiol esters, dimercapto, carboxylic acid, amino acid, organic heterocyclic molecule or inorganic sulphide；Preferably, described
Ligand exchange reagent be selected from 3- mercaptopropionic acid, thioacetic acid, mercaprol, 3- mercaptobutyric acid ethyl ester, 2,3- dimercaptosuccinic acid,
1,4- dimercapto-DL- threitol, lactic acid, L-cysteine, pyridine, Na2One or more of S.
8. method according to claim 1-7, which is characterized in that the mixing carries out at normal temperature.
9. the method according to claim 1, wherein the method also includes following steps: exchange is obtained
Colloidal nanocrystals are dispersed in a solvent, wherein the solvent is selected from polar organic solvent or water.
10. according to the method described in claim 9, it is characterized in that, the polar organic solvent is selected from methanol, ethyl alcohol, isopropyl
One or more of alcohol, acetone, ethyl acetate, N,N-dimethylformamide, dimethyl sulfoxide.
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