CN107055594A - A kind of sulfide nanocrystalline body and preparation method thereof - Google Patents
A kind of sulfide nanocrystalline body and preparation method thereof Download PDFInfo
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- CN107055594A CN107055594A CN201710306907.4A CN201710306907A CN107055594A CN 107055594 A CN107055594 A CN 107055594A CN 201710306907 A CN201710306907 A CN 201710306907A CN 107055594 A CN107055594 A CN 107055594A
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Abstract
The invention provides a kind of preparation method of sulfide nanocrystalline body, with sulphur presoma chemical reaction generation sulfide nanocrystalline body occurs in solution system for lead presoma, and sulphur presoma includes thiocarbonate, and solution system contains amines.Raw material low toxicity, reaction condition used in the present invention is simple, continuously can prepare sulfide nanocrystalline body of the emission peak in 800 2200nm in same batch experiment at low temperature.
Description
Technical field
The present invention relates to nanocrystal preparing technical field, more particularly to a kind of sulfide nanocrystalline body and its preparation side
Method.
Background technology
Sulfide nanocrystalline body is a kind of important group IV-VI near-infrared semi-conducting material, with less direct band gap
(298K:0.41eV) with larger Bohr radius (about 18nm).And sulfide nanocrystalline body has good size-dependent, lead to
Crossing quantum confined effect can realize that sulfide nanocrystalline physical efficiency band is adjustable in the range of visible-near-infrared spectrum.Therefore, vulcanize
Lead nanocrystal has the optical property and electrical properties of uniqueness, in solar cell, infrared acquisition, infrared treatment, heat and life
There is important application value in the fields such as thing imaging.
At present, the main preparation methods of monodisperse pulmbous sulfide nanocrystal are solution colloid chemistry methods.Hines et al.
(Advanced Materials 2003,15,18441849) reports the oil phase synthesis of sulfide nanocrystalline body first, in inertia
Double (trimethyl silicon sulfides) is rapidly injected into 150 DEG C of oleic acid lead solutions obtain monodisperse colloid sulfide nanocrystalline under atmosphere
Body.By changing reaction temperature and reaction time absorption spectrum can be realized in 800-1800nm range regulations.But the method is normal
Using poisonous double (trimethyl silicon sulfides), and need the reaction conditions such as inert atmosphere protection and high temperature and higher boiling.Separately
A kind of outer typical synthetic method is Moreels et al. (ACS Nano 2011,5,2004) under an inert atmosphere to 80-160 DEG C
The octadecenyl amine solution that S powder is rapidly injected in the octadecenyl amine solution of lead chloride obtains monodisperse colloid sulfide nanocrystalline
Body.Absorption light can be realized by adjusting tri-n-octyl phosphine (TOP) solution of addition S powder, changing reaction temperature and reaction time
Spectrum is in 900-2200nm range regulations.But the method has used harmful phosphonate reagent that contains, and needs to adjust whether adding three just
Octyl group phosphine, can not realize wavelength continuously adjustabe, which increase the complexity of production in same batch experiment.Finally, no matter
It is that double (trimethyl silicon sulfides) or tri-n-octyl phosphine are expensive, and is required to fast injection, is not suitable for large-scale production.
Therefore, in the urgent need to a kind of cheap, process of searching is easy, wavelength continuously adjustabe sulfide nanocrystalline body preparation method.
The content of the invention
It is an object of the invention to provide a kind of preparation method of sulfide nanocrystalline body, the preparation method technique is simple,
Raw material low toxicity, it can realize that particle diameter continuously regulates and controls, saves preparation time, raw material and cost in the experiment of same batch at low temperature.
According to an aspect of the invention, there is provided a kind of preparation method of sulfide nanocrystalline body, preparation method includes
Lead presoma occurs chemical reaction with sulphur presoma in solution system and obtains sulfide nanocrystalline body, and sulphur presoma includes thio
Carbonate, solution system contains amines.
Preferably, thiocarbonate is selected from least one of following structural formula compound,
Wherein R1For O or S；R2For O, S, N-R4Or Si-R5R6, R4、R5、R6For H or C1-C18 alkane chain；R3
For C1-C18 alkane chain；N=1,2,3 or 4；M is cation, its constitution element include Li, Na, K, Be, Mg, Ca, Al,
Mn, Fe, Co, Ni, Ti, V, Cu, Zn, Ga, Ag, Cd, In, Sn, Ba, Au or Hg.
Preferably, amines includes saturation of the carbon chain lengths not less than 2 or unsaturated amine.
Preferably, in solution system solvent include boiling point be more than 40 DEG C alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers,
At least one of amine, ketone and esters.
Preferably, the preparation method includes step：S1, by lead compound, the first part, that amines is dissolved in first is molten
In agent, uniform lead precursor solution is formed；S2, addition thiocarbonate solid, the sulphur into the lead precursor solution
For carbonate as the sulphur presoma, the lead presoma obtains sulfide nanocrystalline body with the sulphur forerunner precursor reactant.
Preferably, the preparation method includes step：S1, lead compound, the first part be dissolved in amines, formed
Uniform lead precursor solution；S2, the addition thiocarbonate solid into the lead precursor solution, the thiocarbonate are made
For the sulphur presoma, the lead presoma obtains sulfide nanocrystalline body with the sulphur forerunner precursor reactant.
Preferably, the preparation method includes step：S1, lead compound, the first part be dissolved in the first solvent, formed
Uniform lead precursor solution；S2, the thiocarbonate is dissolved in the second solvent, forms uniform sulphur precursor solution；
At least one of first solvent and second solvent are also dissolved with amines；S3, by the lead precursor solution and institute
The mixing of sulphur precursor solution is stated, the lead presoma obtains sulfide nanocrystalline body with the sulphur forerunner precursor reactant.
Preferably, the preparation method includes step：S1, lead compound, the first part be dissolved in the first solvent, formed
Uniform lead precursor solution；S2, the thiocarbonate is dissolved in the second solvent, forms uniform sulphur precursor solution；
At least one of described first solvent or the second solvent are amines；S3, by before the lead precursor solution and the sulphur
Liquid solution mixing is driven, the lead presoma obtains sulfide nanocrystalline body with the sulphur forerunner precursor reactant.
Preferably, first part include ten acid, undecenoic acid, lauric acid/dodecanoic acid, lauroleic acid, tridecanoic acid, tridecylenic acid,
Tetradecylic acid, tetradecenoic acid, pentadecanoic acid, pentadecylenic acid, hexadecylic acid, gaidic acid, heptadecanoic acid, heptadecenoic acid, stearic acid and 18
At least one of olefin(e) acid.
Preferably, first solvent or second solvent include alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers,
At least one of amine, ketone and esters.
Preferably, the lead compound include lead oxygen compound, lead halide, substitution or the alkyl carboxylic acid lead not replaced,
Substitution or the lead borate, plumbi nitras, substitution or the lead phosphate not replaced that do not replace, lead sulfate, substitution or not
At least one of sulfonic acid lead.
Preferably, the range of reaction temperature of the preparation method is 0-60 DEG C.
Preferably, the range of reaction temperature of the preparation method is 20-50 DEG C.
Preferably, the amines include ethylenediamine, triethylamine, hexylamine, heptyl amice, octylame, trioctylamine, nonyl amine, ten amine,
Ten enamines, undecylamine, hendecene amine, lauryl amine, laurylene amine, tridecyl amine, tridecylene amine, tetradecy lamine, tetradecene amine, 15
At least one of amine, 15 enamines, cetylamine, hexadecylene amine, heptadecyl-amine, 17 enamines, octadecylamine and octadecenyl amine.
There is provided a kind of sulfide nanocrystalline body, the emission peak of sulfide nanocrystalline body according to another aspect of the present invention
Between 800-2200nm, sulfide nanocrystalline body is made by above-mentioned preparation method.
The invention has the advantages that：The present invention can be prepared at low temperature using thiocarbonate as sulphur presoma
Sulfide nanocrystalline body, different chis can be obtained by changing temperature, consumption of precursor for reacting etc. in the experiment of same batch
High-quality sulfide nanocrystalline body of the very little, emission peak in 800-2200nm.
Brief description of the drawings
Fig. 1 is the fluorescence emission spectrogram of compound of the sulfide nanocrystalline body prepared in the embodiment of the present invention；
Fig. 2 is the transmission electron microscope figure of the sulfide nanocrystalline body prepared in the embodiment of the present invention.
Embodiment
Below in conjunction with embodiment of the present invention, the technical scheme in the embodiment of the present invention is described in detail, shown
So, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other implementation that those of ordinary skill in the art are obtained on the premise of creative work is not made
Mode, belongs to the scope of the present invention.
The invention provides a kind of preparation method of sulfide nanocrystalline body, preparation method includes lead presoma and sulphur forerunner
Chemical reaction occurs in solution system and obtains sulfide nanocrystalline body for body, and sulphur presoma includes thiocarbonate, solution system
Contain amines.
In one preferred embodiment, thiocarbonate is selected from least one of following structural formula compound,
Wherein R1For O or S；R2For O, S, N-R4Or Si-R5R6, R4、R5、R6For H or C1-C18 alkane chain；R3
For C1-C18 alkane chain；N=1,2,3 or 4；M is cation, its constitution element include Li, Na, K, Be, Mg, Ca, Al,
Mn, Fe, Co, Ni, Ti, V, Cu, Zn, Ga, Ag, Cd, In, Sn, Ba, Au or Hg.
In one preferred embodiment, R1For O, because O atom has stronger electron-withdrawing power, effectively reduce
The intensity of C-S keys, adds it as the reactivity in S sources.Another preferred embodiment in, R1For S, R1Can be with
It is used as the sulphur source of reaction.Cation M is preferably Li, Na, K, Zn, Mg, Ca or Al.
In one preferred embodiment, R1For S, R2For O.In one preferred embodiment, thiocarbonate bag
Include xanthopone, ehtyl potassium xanthate, xanthogen zinc, xanthogen potassium, zinc butyl xanthate and butyl xanthan
At least one of sour potassium.
The use of amines adds dispersing uniformity and vulcanized lead nanometer of the thiocarbonate in solution system
The generating rate of crystal, meanwhile, amines acts not only as the complex of thiocarbonate, is also used as vulcanized lead and receives
The ligand groups on surface after prepared by meter Jing Ti.Amines is preferably saturation of the carbon chain lengths not less than 2 or unsaturated amine.
One preferred embodiment in, amines include ethylenediamine, triethylamine, hexylamine, heptyl amice, octylame, trioctylamine, nonyl amine, ten
Amine, ten enamines, undecylamine, hendecene amine, lauryl amine, laurylene amine, tridecyl amine, tridecylene amine, tetradecy lamine, tetradecene amine, ten
At least one of five amine, 15 enamines, cetylamine, hexadecylene amine, heptadecyl-amine, 17 enamines, octadecylamine and octadecenyl amine.This
The technical staff in field can be selected amines according to actual conditions.
The boiling point of solvent should be more than the temperature of reaction in solution system.To adapt to the reaction temperature of wide scope, solution body
Solvent is preferably included in alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone and esters of the boiling point more than 40 DEG C in system
At least one, more preferably boiling point be more than 100 DEG C alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone
At least one of with esters.In a specific embodiment, solvent is octadecylene；In another specific embodiment
In, solvent is atoleine.
There are numerous embodiments in the method that the present invention prepares nanocrystal in solution system.
In one preferred embodiment, preparation method includes step：S1, by lead compound, the first part and amination
Compound is dissolved in the first solvent, forms uniform lead precursor solution, and first solvent includes alkane, alkene, halogenated hydrocarbons, virtue
At least one of fragrant hydrocarbon, ethers, amine, ketone and esters, first part include ten acid, undecenoic acid, lauric acid/dodecanoic acid, ten
Dienoic acid, tridecanoic acid, tridecylenic acid, tetradecylic acid, tetradecenoic acid, pentadecanoic acid, pentadecylenic acid, hexadecylic acid, gaidic acid, 17
At least one of acid, heptadecenoic acid, stearic acid and octadecenic acid；S2, the thiocarbonate is dissolved in the second solvent, shape
Into uniform sulphur precursor solution, second solvent include alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone and
At least one of esters；S3, the lead precursor solution mixed with the sulphur precursor solution, the lead presoma and institute
State sulphur forerunner's precursor reactant and obtain sulfide nanocrystalline body.By way of lead compound and thiocarbonate are prepared into solution,
It is more beneficial for controlling the addition and dispersing uniformity of presoma in course of reaction.In one preferred embodiment, lead
Compound, the first part are dissolved in the first solvent simultaneously or successively.Another preferred embodiment in, lead compound with
After first part is compatible, then it is re-dissolved in the first solvent.Thiocarbonate in following structural formula compound at least one
Kind,
Wherein R1For O or S；R2For O, S, N-R4Or Si-R5R6, R4、R5、R6For H or C1-C18 alkane chain；R3
For C1-C18 alkane chain；N=1,2,3 or 4；M is cation, its constitution element include Li, Na, K, Be, Mg, Ca, Al,
Mn, Fe, Co, Ni, Ti, V, Cu, Zn, Ga, Ag, Cd, In, Sn, Ba, Au or Hg.
Another preferred embodiment in, preparation method include step：S1, lead compound, the first part be dissolved in
In first solvent, uniform lead precursor solution is formed, first solvent is amine, and first part includes ten acid, ten
Monoenoic acid, lauric acid/dodecanoic acid, lauroleic acid, tridecanoic acid, tridecylenic acid, tetradecylic acid, tetradecenoic acid, pentadecanoic acid, pentadecylenic acid, 16
At least one of acid, gaidic acid, heptadecanoic acid, heptadecenoic acid, stearic acid and octadecenic acid；S2, by the thiocarbonate
It is dissolved in the second solvent, forms uniform sulphur precursor solution, second solvent includes alkane, alkene, halogenated hydrocarbons, fragrance
At least one of hydrocarbon, ethers, amine, ketone and esters；S3, the lead precursor solution mixed with the sulphur precursor solution
Close, the lead presoma obtains sulfide nanocrystalline body with the sulphur forerunner precursor reactant.Thiocarbonate is selected from following structural formula
At least one of compound,
Wherein R1For O or S；R2For O, S, N-R4Or Si-R5R6, R4、R5、R6For H or C1-C18 alkane chain；R3
For C1-C18 alkane chain；N=1,2,3 or 4；M is cation, its constitution element include Li, Na, K, Be, Mg, Ca, Al,
Mn, Fe, Co, Ni, Ti, V, Cu, Zn, Ga, Ag, Cd, In, Sn, Ba, Au or Hg.
Another preferred embodiment in, preparation method include step：S1, lead compound, the first part be dissolved in
In first solvent, uniform lead precursor solution is formed, first solvent includes alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ether
At least one of class, amine, ketone and esters, first part include ten acid, undecenoic acid, lauric acid/dodecanoic acid, lauroleic acid,
Tridecanoic acid, tridecylenic acid, tetradecylic acid, tetradecenoic acid, pentadecanoic acid, pentadecylenic acid, hexadecylic acid, gaidic acid, heptadecanoic acid, 17 alkene
At least one of acid, stearic acid and octadecenic acid；S2, the thiocarbonate and amines be dissolved in the second solvent,
Uniform sulphur precursor solution is formed, second solvent includes alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone
At least one of with esters；S3, the lead precursor solution mixed with the sulphur precursor solution, the lead presoma with
The sulphur forerunner precursor reactant obtains sulfide nanocrystalline body.Thiocarbonate in following structural formula compound at least one
Kind,
Wherein R1For O or S；R2For O, S, N-R4Or Si-R5R6, R4、R5、R6For H or C1-C18 alkane chain；R3
For C1-C18 alkane chain；N=1,2,3 or 4；M is cation, its constitution element include Li, Na, K, Be, Mg, Ca, Al,
Mn, Fe, Co, Ni, Ti, V, Cu, Zn, Ga, Ag, Cd, In, Sn, Ba, Au or Hg.
Another preferred embodiment in, preparation method include step：S1, lead compound, the first part be dissolved in
In first solvent, uniform lead precursor solution is formed, first solvent includes alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ether
At least one of class, amine, ketone and esters, first part include ten acid, undecenoic acid, lauric acid/dodecanoic acid, lauroleic acid,
Tridecanoic acid, tridecylenic acid, tetradecylic acid, tetradecenoic acid, pentadecanoic acid, pentadecylenic acid, hexadecylic acid, gaidic acid, heptadecanoic acid, 17 alkene
At least one of acid, stearic acid and octadecenic acid；S2, the thiocarbonate is dissolved in the second solvent, forms uniform
Sulphur precursor solution, second solvent is amine；S3, the lead precursor solution mixed with the sulphur precursor solution,
The lead presoma obtains sulfide nanocrystalline body with the sulphur forerunner precursor reactant.Thiocarbonate is selected from following structural formula chemical combination
At least one of thing,
Wherein R1For O or S；R2For O, S, N-R4Or Si-R5R6, R4、R5、R6For H or C1-C18 alkane chain；R3
For C1-C18 alkane chain；N=1,2,3 or 4；M is cation, its constitution element include Li, Na, K, Be, Mg, Ca, Al,
Mn, Fe, Co, Ni, Ti, V, Cu, Zn, Ga, Ag, Cd, In, Sn, Ba, Au or Hg.
Another preferred embodiment in, preparation method include step：S1, by lead compound, the first part and amine
Compound is dissolved in the first solvent, forms uniform lead precursor solution, first solvent include alkane, alkene, halogenated hydrocarbons,
At least one of aromatic hydrocarbon, ethers, amine, ketone and esters, first part include ten acid, undecenoic acid, lauric acid/dodecanoic acid,
Lauroleic acid, tridecanoic acid, tridecylenic acid, tetradecylic acid, tetradecenoic acid, pentadecanoic acid, pentadecylenic acid, hexadecylic acid, gaidic acid, 17
At least one of acid, heptadecenoic acid, stearic acid and octadecenic acid；S2, add into the lead precursor solution it is described thio
Carbonate solid, reaction obtains sulfide nanocrystalline body.Thiocarbonate is selected from least one of following structural formula compound,
Wherein R1For O or S；R2For O, S, N-R4Or Si-R5R6, R4、R5、R6For H or C1-C18 alkane chain；R3
For C1-C18 alkane chain；N=1,2,3 or 4；M is cation, its constitution element include Li, Na, K, Be, Mg, Ca, Al,
Mn, Fe, Co, Ni, Ti, V, Cu, Zn, Ga, Ag, Cd, In, Sn, Ba, Au or Hg.
Another preferred embodiment in, preparation method include step：S1, lead compound, the first part be dissolved in
In first solvent, uniform lead precursor solution is formed, first solvent is amine, and first part includes ten acid, ten
Monoenoic acid, lauric acid/dodecanoic acid, lauroleic acid, tridecanoic acid, tridecylenic acid, tetradecylic acid, tetradecenoic acid, pentadecanoic acid, pentadecylenic acid, 16
At least one of acid, gaidic acid, heptadecanoic acid, heptadecenoic acid, stearic acid and octadecenic acid；It is S2, molten to the lead presoma
The thiocarbonate solid is added in liquid, reaction obtains sulfide nanocrystalline body.Thiocarbonate is selected from following structural formula
At least one of compound,
Wherein R1For O or S；R2For O, S, N-R4Or Si-R5R6, R4、R5、R6For H or C1-C18 alkane chain；R3
For C1-C18 alkane chain；N=1,2,3 or 4；M is cation, its constitution element include Li, Na, K, Be, Mg, Ca, Al,
Mn, Fe, Co, Ni, Ti, V, Cu, Zn, Ga, Ag, Cd, In, Sn, Ba, Au or Hg.
Lead compound preferably include lead oxygen compound, lead halide, substitution or the alkyl carboxylic acid lead not replaced, substitution or
In the lead borate, plumbi nitras, substitution or the lead phosphate not replaced that do not replace, lead sulfate, substitution or the sulfonic acid lead that does not replace
At least one.In one preferred embodiment, lead compound includes at least one in lead oxide, lead chloride, lead acetate
Kind.
In order to obtain the product of different emission and size, after the preparation of sulfide nanocrystalline body, body is additionally included in
The lead precursor solution and/or thiocarbonate prepared, lead precursor solution and/or thiocarbonate are further added in system
Addition can according to different sized nanocrystals formational theory values calculate obtain.In one preferred embodiment, in advance
The required forerunner's scale of construction for determining the sulfide nanocrystalline body of launch wavelength is added by multiple batches of, while anti-in presoma adition process
Temperature is answered gradually to increase.
The shortcoming that vulcanized lead needs hot conditions to prepare can be avoided by technical scheme, meanwhile, low temperature is more
Be conducive to controlling the size of sulfide nanocrystalline body.In one preferred embodiment, what prepared by sulfide nanocrystalline body is anti-
Temperature is answered at 0-60 DEG C, can specifically include 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, more preferably 60 DEG C, 20-
50℃.At relatively low temperature, such as 0 DEG C -20 DEG C when, the generating rate of sulfide nanocrystalline body is slow, is conducive to small size nanometer
The preparation of crystal；At a relatively high temperature, such as 40 DEG C -60 DEG C when, the generating rate of sulfide nanocrystalline body is fast, is conducive to big chi
The preparation of very little nanocrystal.With the size increase of sulfide nanocrystalline body, increase temperature is conducive to the generation of nanocrystal,
One preferred embodiment in, reaction temperature is gradually increased to 60 DEG C by 20 DEG C.
To improve the optical property of nanocrystal, after sulfide nanocrystalline body is prepared, in addition to unreacted original is removed
The step of material and other impurities, specifically include separation, purification.
According to the typical embodiment of the present invention, the invention provides a kind of sulfide nanocrystalline body, vulcanized lead is received
Meter Jing Ti emission peak can cover the whole wave-length coverages commonly used in current near-infrared field between 800-2200nm.
Embodiment 1
S1, prepare lead precursor solution：
Take in 4 mMs of (mmol) PbO, 8 milliliters of oleic acid (OA) and 35mL octadecylene and 100mL glass container and mix
Close, under inert atmosphere, stirring is completely dissolved it, is prepared into lead precursor solution, is stored in standby in nitrogen inert atmosphere；
S2, prepare sulphur precursor solution：
The lauryl amine of 0.2g xanthopone, 30mL octadecylene and 2mL is taken to be mixed in 100mL glass container
Close, under inert atmosphere, stirring is completely dissolved it, is prepared into sulphur precursor solution, is stored in standby in nitrogen atmosphere；
S3, sulfide nanocrystalline body preparation：
The Pb (OA) prepared in the S1 for taking 10mL2The xanthopone prepared in solution, disposable injection 2.5mL S2
Solution, 20 DEG C or so stirrings, solution is gradually changed into faint yellow and is ultimately become black from colourless, prepares sulfide nanocrystalline
Body, its fluorescence emission spectrum of sampling and testing.
Embodiment 2
Same as Example 1, different is, after S3, further, and reaction temperature is gradually risen to 25 DEG C,
While temperature is raised, a certain amount of ethoxy-dithioformic acid zinc solution and/or Pb (OA) is added dropwise2Solution, samples after reaction and surveys
Try its fluorescence emission spectrum.
Embodiment 3
Same as Example 2, different is, further, and reaction temperature is gradually risen to 30 DEG C, in rise temperature
While spending, a certain amount of ethoxy-dithioformic acid zinc solution and/or Pb (OA) is added dropwise2Its fluorescence of sampling and testing after solution, reaction
Emission spectrum.
Embodiment 4
Same as Example 3, different is, further, and reaction temperature is gradually risen to 35 DEG C, in rise temperature
While spending, a certain amount of ethoxy-dithioformic acid zinc solution and/or Pb (OA) is added dropwise2Its fluorescence of sampling and testing after solution, reaction
Emission spectrum.
Embodiment 5
Same as Example 4, different is, further, and reaction temperature is gradually risen to 40 DEG C, in rise temperature
While spending, a certain amount of ethoxy-dithioformic acid zinc solution and/or Pb (OA) is added dropwise2Its fluorescence of sampling and testing after solution, reaction
Emission spectrum.
Embodiment 6
Same as Example 5, different is, further, and reaction temperature is gradually risen to 50 DEG C, in rise temperature
While spending, a certain amount of ethoxy-dithioformic acid zinc solution and/or Pb (OA) is added dropwise2Its fluorescence of sampling and testing after solution, reaction
Emission spectrum.
Embodiment 7
Same as Example 6, different is, further, and reaction temperature is gradually risen to 60 DEG C, in rise temperature
While spending, a certain amount of ethoxy-dithioformic acid zinc solution and/or Pb (OA) is added dropwise2Its fluorescence of sampling and testing after solution, reaction
Emission spectrum.
Fig. 1 is visible with reaction raw materials in the fluorescence emission spectrogram of compound of the sampling and testing into embodiment 7 of embodiment 1, figure
Addition, sulfide nanocrystalline body emission peak from 820nm red shifts to 1570nm at.For those skilled in the art, may be used
With it is intended that when adding more sulphur presomas and lead presoma, the emission peak of sulfide nanocrystalline body can be further red
Move.Fig. 2 is the transmission electron microscope figure of sulfide nanocrystalline body of the emission peak prepared in embodiment 7 at 1570nm,
Test result indicates that its pattern is uniform, Size Distribution is homogeneous.
The present invention can prepare sulfide nanocrystalline body, present invention system at low temperature using thiocarbonate as sulphur presoma
Standby process is simple, easy control of reaction conditions, and covering wave-length coverage can be prepared in the experiment of same batch in 800-2200nm
The sulfide nanocrystalline body of scope or more red shift.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in protection scope of the present invention.
Claims (15)
1. a kind of preparation method of sulfide nanocrystalline body, the preparation method includes lead presoma with sulphur presoma in solution body
Chemical reaction occurs in system and obtains the sulfide nanocrystalline body, it is characterised in that the sulphur presoma includes thiocarbonate,
The solution system contains amines.
2. preparation method according to claim 1, it is characterised in that：The thiocarbonate is selected from following structural formula chemical combination
At least one of thing,
Wherein R1For O or S；R2For O, S, N-R4Or Si-R5R6, R4、R5、R6For H or C1-C18 alkane chain；R3For C1-
C18 alkane chain；N=1,2,3 or 4；M is cation, its constitution element include Li, Na, K, Be, Mg, Ca, Al, Mn, Fe,
Co, Ni, Ti, V, Cu, Zn, Ga, Ag, Cd, In, Sn, Ba, Au or Hg.
3. preparation method according to claim 1, it is characterised in that：The amines includes carbon chain lengths and is not less than 2
Saturation or unsaturated amine.
4. preparation method according to claim 1, it is characterised in that：Solvent includes boiling point and is more than 40 in the solution system
DEG C at least one of alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone and esters.
5. preparation method according to claim 1, it is characterised in that：The preparation method includes step：
S1, lead compound, the first part, amines be dissolved in the first solvent, form uniform lead precursor solution；
S2, into the lead precursor solution add thiocarbonate solid, the thiocarbonate as the sulphur presoma,
The lead presoma obtains sulfide nanocrystalline body with the sulphur forerunner precursor reactant.
6. preparation method according to claim 1, it is characterised in that：The preparation method includes step：
S1, lead compound, the first part be dissolved in amines, form uniform lead precursor solution；
S2, into the lead precursor solution add thiocarbonate solid, the thiocarbonate as the sulphur presoma,
The lead presoma obtains sulfide nanocrystalline body with the sulphur forerunner precursor reactant.
7. preparation method according to claim 1, it is characterised in that：The preparation method includes step：
S1, lead compound, the first part be dissolved in the first solvent, form uniform lead precursor solution；
S2, the thiocarbonate is dissolved in the second solvent, forms uniform sulphur precursor solution；
At least one of first solvent and second solvent are also dissolved with amines；
S3, the lead precursor solution mixed with the sulphur precursor solution, the lead presoma and the sulphur presoma are anti-
Sulfide nanocrystalline body should be obtained.
8. preparation method according to claim 1, it is characterised in that：The preparation method includes step：
S1, lead compound, the first part be dissolved in the first solvent, form uniform lead precursor solution；
S2, the thiocarbonate is dissolved in the second solvent, forms uniform sulphur precursor solution；
At least one of described first solvent or the second solvent are amines；
S3, the lead precursor solution mixed with the sulphur precursor solution, the lead presoma and the sulphur presoma are anti-
Sulfide nanocrystalline body should be obtained.
9. the preparation method according to claim 5,6,7 or 8, it is characterised in that：First part include ten acid,
Undecenoic acid, lauric acid/dodecanoic acid, lauroleic acid, tridecanoic acid, tridecylenic acid, tetradecylic acid, tetradecenoic acid, pentadecanoic acid, pentadecylenic acid, 16
At least one of acid, gaidic acid, heptadecanoic acid, heptadecenoic acid, stearic acid and octadecenic acid.
10. the preparation method according to claim 5,7 or 8, it is characterised in that：First solvent or described
Two solvents include at least one of alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone and esters.
11. the preparation method according to claim 5,6,7 or 8, it is characterised in that the lead compound includes lead oxygen
Compound, lead halide, substitution or the alkyl carboxylic acid lead not replaced, substitution or do not replace lead borate, plumbi nitras, substitution or
At least one of lead phosphate that person does not replace, lead sulfate, substitution or sulfonic acid lead for not replacing.
12. the preparation method according to claim 1,5,6,7 or 8, it is characterised in that：The reaction temperature of the preparation method
It is 0-60 DEG C to spend scope.
13. preparation method according to claim 12, it is characterised in that：The range of reaction temperature of the preparation method is
20-50℃。
14. the preparation method according to claim 1,5,6,7 or 8, it is characterised in that：The amines includes second two
Amine, triethylamine, hexylamine, heptyl amice, octylame, trioctylamine, nonyl amine, ten amine, ten enamines, undecylamine, hendecene amine, lauryl amine, 12
Enamine, tridecyl amine, tridecylene amine, tetradecy lamine, tetradecene amine, pentadecyl amine, 15 enamines, cetylamine, hexadecylene amine, heptadecyl-amine,
At least one of 17 enamines, octadecylamine and octadecenyl amine.
15. a kind of sulfide nanocrystalline body, the emission peak of the sulfide nanocrystalline body is between 800-2200nm, and its feature exists
In the sulfide nanocrystalline body any methods described in claim 1-14 is made.
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| 王美娟: ""硫化铅和硫化亚锡微纳米晶的制备及表征"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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| CN109850937A (en) * | 2019-01-25 | 2019-06-07 | 深圳扑浪创新科技有限公司 | A kind of preparation method of vulcanized lead quantum dot fluorescence powder |
| CN109850937B (en) * | 2019-01-25 | 2022-03-25 | 深圳扑浪创新科技有限公司 | Preparation method of lead sulfide quantum dot fluorescent powder |
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