CN105776320B - A kind of preparation method of copper-zinc-tin-sulfur nano particle of vitamin C parcel and products thereof - Google Patents
A kind of preparation method of copper-zinc-tin-sulfur nano particle of vitamin C parcel and products thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of the copper-zinc-tin-sulfur nano particle of vitamin C parcel, source metal, vitamin C are mixed with dimethyl sulfoxide (DMSO), obtain source metal solution；Described source metal is metal chloride or metal acetate salt；Sulphur source is mixed with the mixed solvent of proton solvent/dimethyl sulfoxide (DMSO) again, obtains sulphur source solution；Described sulphur source is vulcanized sodium, ethyl mercaptan or thiocarbamide；Finally described sulphur source solution is added drop-wise in source metal solution, after reacting 2~20h at 100~180 DEG C, is centrifuged obtaining the copper-zinc-tin-sulfur nano particle of vitamin C parcel.The present invention provides a kind of preparation method of the copper-zinc-tin-sulfur nano particle of vitamin C parcel, carries out at ambient pressure, reaction condition is gentle, process control, is adapted to large-scale industrial production.It is prepared using vitamin C as part, the copper-zinc-tin-sulfur nano particle of the kesterite crystal formation of parcel.
Description
Technical field
The present invention relates to field of nano material preparation, and in particular to a kind of copper-zinc-tin-sulfur nano particle of vitamin C parcel
Preparation method and products thereof.
Background technology
Copper-zinc-tin-sulfur nano particle is important hull cell light absorbent, has outstanding physicochemical characteristics, such as may be used
The band gap (1.0~1.5eV) of regulation, high absorptivity (about 104cm-1), it is non-toxic, metallic element be all it is cheap and
Earth mass storage, can a large amount of industrialized productions.
The copper-zinc-tin-sulfur nano particle of long-chain Ligand parcel, it is especially wide as the nano particle of part using oleyl amine and oleic acid
(Phys.Chem.Chem.Phys., 2012,14,8090-8096 are studied generally；RSC Adv.,2013,3,5845-5850；
J.Am.Chem.Soc.,2009,131,12554-12555).But the steric hindrance of long-chain Ligand is bigger, and it is wrapped in nanometer
Brilliant surface can cause very big negative effect to nanocrystalline charge transport quality.Although the big long-chain Ligand of these steric hindrances
Can be by ligand exchange by short chain ligand substituting, but ligand exchange condition is harsh, easily reunites after exchange and exchanges endless
Entirely.
The copper zinc-tin of the small short chain part of steric hindrance (such as PVP, triethanolamine, thioacetamide and ethylenediamine etc.) parcel
Sulphur nano particle also possesses some special knowledge (J.Mater.Chem., 2012,22,6553-6555 at present；J.Phys.Chem.C,2011,
115,19632-19639).In addition to PVP toxicity very littles, remaining organic amine part usually contains stronger toxicity, they
Not only olfactory threshold limit value is low, also tend to be Carcinogenic Nitrosamines precursor.
(the solvent-thermal methods such as Cai Qian, Liang Xiaojuan, Zhong Jiasong prepare spherical Cu to Cai Qian etc.2ZnSnS4Nanocrystalline and its sign) it is logical
Cross the Cu of solvent structure custerite structure2ZnSnS4It is nanocrystalline, using Cys as silicon source and complexing agent,
Using metal chloride as presoma, in autoclave, 16h is reacted at 180 DEG C, obtains Cu2ZnSnS4Microballoon.This method
Cys are employed as silicon source and complexing agent, but the reaction is still to carry out under elevated pressure conditions, and this is undoubtedly unfavorable for greatly
The industrialized production of scale.
(Zhang Meijuan, Liu Jingbing, Zong Kai, Wang Hao, Sun Yuxiu, the Yan Hui .Cu such as Zhang Meijuan2ZnSnS4The preparation of nano-crystalline microsphere
And its Chinese Journal of Inorganic Chemistries are characterized, and 2013.2) it have studied Cu2ZnSnS4The preparation of nano-crystalline microsphere, and specifically disclose by 2:
2:1:8 stoichiometric proportion weighs copper chloride, zinc chloride, stannic chloride and thiocarbamide, is added sequentially in ethylene glycol, is placed in high pressure
In kettle, Cu is prepared through solvent thermal reaction at 180 DEG C2ZnSnS4Nano-crystalline microsphere.Using ethylene glycol as solvent in the preparation method,
But need to prepare Cu through solvent thermal reaction under elevated pressure conditions2ZnSnS4Nano-crystalline microsphere.
The content of the invention
The present invention provides a kind of preparation method of the copper-zinc-tin-sulfur nano particle of vitamin C parcel, carries out at ambient pressure, instead
Mild condition, process control are answered, is adapted to large-scale industrial production.
A kind of preparation method of the copper-zinc-tin-sulfur nano particle of vitamin C parcel, comprises the following steps：
(1) mixed source metal with the vitamin C as part and dimethyl sulfoxide (DMSO) (DMSO), obtain source metal solution；
Described source metal is metal chloride or metal acetate salt；
(2) sulphur source is mixed with the mixed solvent of proton solvent/dimethyl sulfoxide (DMSO), obtains sulphur source solution；
Described sulphur source is vulcanized sodium, ethyl mercaptan or thiocarbamide；
(3) described sulphur source solution is added drop-wise in source metal solution, after reacting 2~20h at 100~180 DEG C, through centrifugation
The copper-zinc-tin-sulfur nano particle of isolated vitamin C parcel.
The present invention selects special proton solvent/dimethyl sulfoxide (DMSO) mixed solvent, and with specific sulphur source and source metal
Match somebody with somebody, in the presence of vitamin C, realize the synchronous growth of source metal and sulphur source, obtain the copper-zinc-tin-sulfur nano particle of high-purity.
By the double action of solvent and part, the possibility that multiple element under temperate condition is collectively forming single crystal structure is realized,
Avoid the use of the long-chain Ligand of high temperature injection method and the use of hydro-thermal method high temperature high pressure harsh conditions.
Preferably, in step (1), in the source metal solution, the concentration in copper source is 10~50mmol/L, zinc source it is dense
Spend for 5~25mmol/L, the concentration of tin source is 5~25mmol/L；Further preferably, the concentration of copper source, zinc source and tin source
Than for 2:1:1.
Ascorbic concentration has an impact to the stability of nano particle in the present invention, preferably, in step (1), it is described
Ascorbic concentration is 10~50mmol/L in source metal solution；Further preferably, copper source and ascorbic concentration ratio
For 1:1.
The concentration of sulphur source has considerable influence to the uniform particle diameter of nano particle, preferably, in step (2), the sulphur
The concentration of source solution is 10~50mmol/L.
Preferably, in step (2), described proton solvent is methanol, ethanol or water, proton solvent and dimethyl sulfoxide (DMSO)
Volume ratio be 1:1~10；The volume ratio of further preferred proton solvent and dimethyl sulfoxide (DMSO) is 1:10；Still further preferably,
Described mixed solvent is ethanol/dimethyl sulfoxide (DMSO).Proton solvent is molten as reaction as hydrotropy solvent, DMSO in reaction system
Agent, according to sulphur source in the mixed solvent solubility difference, it is appropriate to adjust proton solvent and DMSO ratio in sulphur source solution.
Preferably, in step (3), the volume ratio of source metal solution and sulphur source solution is 1:1~5.
Preferably, in step (3), the time that described sulphur source solution is added drop-wise in source metal solution is 1min~4h,
More preferably 5~60min.
In the presence of vitamin C, the mixed solvent of proton solvent/dimethyl sulfoxide (DMSO) and the matching of source metal and sulphur source,
The synchronous growth of source metal and sulphur source can be realized, obtains the copper-zinc-tin-sulfur nano particle of high-purity.Most preferably：
In the source metal solution, the concentration in copper source is 31.25mmol/L, and the concentration ratio in copper source, zinc source and tin source is 2:
1:1, copper source is 1 with ascorbic concentration ratio:1；
The concentration of described sulphur source solution is 20~50mmol/L, using proton solvent/dimethyl sulfoxide (DMSO) as mixed solvent, matter
The volume ratio of sub- solvent and dimethyl sulfoxide (DMSO) is 1:10；
It is 1 by the volume ratio of source metal solution and sulphur source solution:Reaction obtains dimension life at 1.25~2.75,150~155 DEG C
The copper-zinc-tin-sulfur nano particle of plain C parcels.
The copper-zinc-tin-sulfur nano particle of vitamin C that a kind of preparation method described in basis obtains parcel, using vitamin C as
Part, particle diameter are 5~100nm, and described copper-zinc-tin-sulfur nano particle is kesterite crystal formation, chemical formula Cu2ZnSnS4。
Compared with prior art, the present invention has advantages below：
1) present invention is using vitamin C as part, and filters out specific source metal and sulphur source by lot of experiments, with proton
The mixed solvent of solvent/dimethyl sulfoxide (DMSO) is mutually matched, without sealing, the maximum conditions of high pressure, you can obtain regular appearance, grain
The copper-zinc-tin-sulfur nano particle of the homogeneous vitamin C parcel in footpath；And required each material toxicity is small, source is wide, and cost is low, reaction
Mild condition, process control, a brand-new approach is provided for the large-scale industrial production of copper-zinc-tin-sulfur nano particle；
2) the copper-zinc-tin-sulfur nano particle for the vitamin C parcel that prepared by the present invention, the nontoxicity of part, and nanometer are realized
Good dispersion, there is smaller steric hindrance, be easy to leave away, have in electricity material and optical material application and well should
Use prospect.
Brief description of the drawings
Fig. 1 is the XRD of the copper-zinc-tin-sulfur nano particle of vitamin C parcel prepared by embodiment 1；
Fig. 2 is the SEM figures of the copper-zinc-tin-sulfur nano particle of vitamin C parcel prepared by embodiment 1；
Fig. 3 is the UV collection of illustrative plates of the copper-zinc-tin-sulfur nano particle of vitamin C parcel prepared by embodiment 1.
Embodiment
In order to be better understood from the present invention, the solution of the present invention is expanded on further with reference to embodiment, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
By 1.25mmol copper acetates, 0.625mmol zinc chloride, 0.625mmol stannic chlorides and 1.25mmol vitamin Cs are dissolved in
In 40mL DMSO solvents, 155 DEG C are warming up to；Meanwhile 2.5mmol vulcanized sodium is dissolved in 5mL ethanol and 50mL DMSO mixing
In solvent；Then, sodium sulfide solution is instilled into source metal solution, 10min is dripped off；150 DEG C of maintenance reaction temperature, react 6h.With
Acetone avales copper-zinc-tin-sulfur nano particle to come, and centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL
Acetone, centrifugation, produce the copper-zinc-tin-sulfur nano particle that pure vitamin C wraps up.Its XRD is as shown in Figure 1.Synthesized copper
Zinc-tin sulphur nano particle is kesterite crystal formation, is consistent with XRD standard card JCPDS No.26-0575.Fig. 2 is this implementation
The scanning electron microscope (SEM) photograph of the copper-zinc-tin-sulfur nano particle of vitamin C parcel prepared by example, the particle to become clear in figure is copper-zinc-tin-sulfur
Nanocrystalline, particle size is substantially distributed in 20-60nm scopes, is irregular spherical.Fig. 3 is vitamin manufactured in the present embodiment
The UV curves of the copper-zinc-tin-sulfur nano particle of C parcels, it can be seen that play peak position probably in 900nm or so.Can be with by UV curves
It is about 1.3eV to calculate the nanocrystalline edge energy of synthesized copper-zinc-tin-sulfur.
Embodiment 2
By 1.25mmol copper acetates, 0.625mmol zinc chloride, 0.625mmol stannic chlorides and 1.25mmol vitamin Cs are dissolved in
In 40mL DMSO, 155 DEG C are warming up to；Meanwhile 2.5mmol vulcanized sodium is dissolved in 5mL water and 50mL DMSO in the mixed solvent；
Then, sodium sulfide solution is instilled into source metal solution, 10min is dripped off；150 DEG C of maintenance reaction temperature, react 1h.With acetone by copper
Zinc-tin sulphur nano particle, which avales, to be come, and centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL acetone, from
The heart, produce the copper-zinc-tin-sulfur nano particle of pure vitamin C parcel.
Embodiment 3
By 1.25mmol copper acetates, 0.625mmol zinc chloride, 0.625mmol stannic chlorides and 1.25mmol vitamin Cs are dissolved in
In 40mL DMSO, 155 DEG C are warming up to；Meanwhile 2.5mmol vulcanized sodium is dissolved in 5mL methanol and 50mL DMSO mixed solvent
In；Then, sodium sulfide solution is instilled into source metal solution, 10min is dripped off；150 DEG C of maintenance reaction temperature, react 6h.Use acetone
Copper-zinc-tin-sulfur nano particle is avaled to come, centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL third
Ketone, centrifugation, produce the copper-zinc-tin-sulfur nano particle that pure vitamin C wraps up.
Embodiment 4
By 1.25mmol copper chlorides, 0.625mmol zinc chloride, 0.625mmol stannic chlorides and 1.25mmol vitamin Cs are dissolved in
In 40mL DMSO, 155 DEG C are warming up to；Meanwhile 2.5mmol vulcanized sodium is dissolved in 5mL ethanol and 50mL DMSO mixed solvent
In；Then, sodium sulfide solution is instilled into source metal solution, 20min is dripped off；150 DEG C of maintenance reaction temperature, react 12h.Use acetone
Copper-zinc-tin-sulfur nano particle is avaled to come, centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL third
Ketone, centrifugation, produce the copper-zinc-tin-sulfur nano particle that pure vitamin C wraps up.
Embodiment 5
By 1.25mmol copper acetates, 0.625mmol zinc sulfate, 0.625mmol stannic chlorides and 1.25mmol vitamin Cs are dissolved in
In 40mL DMSO, 155 DEG C are warming up to；Meanwhile 2.5mmol vulcanized sodium is dissolved in 5mL ethanol and 50mL DMSO mixed solvent
In；Then, sodium sulfide solution is instilled into source metal solution, 10min is dripped off；150 DEG C of maintenance reaction temperature, react 20h.Use acetone
Copper-zinc-tin-sulfur nano particle is avaled to come, centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL third
Ketone, centrifugation, produce the copper-zinc-tin-sulfur nano particle that pure vitamin C wraps up.
Embodiment 6
1.25mmol copper acetates, 0.625mmol zinc chloride, 0.625mmol stannous chlorides and 1.25mmol vitamin Cs is molten
In 40mL DMSO, 115 DEG C are warming up to；Meanwhile the mixing that 2.5mmol vulcanized sodium is dissolved in 5mL ethanol and 50mL DMSO is molten
In agent；Then, sodium sulfide solution is instilled into source metal solution, 10min is dripped off；110 DEG C of maintenance reaction temperature, react 6h.With third
Ketone avales copper-zinc-tin-sulfur nano particle to come, and centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL third
Ketone, centrifugation, produce the copper-zinc-tin-sulfur nano particle that pure vitamin C wraps up.
Embodiment 7
1.25mmol copper acetates, 0.625mmol zinc sulfate, 0.625mmol stannous chlorides and 1.25mmol vitamin Cs is molten
In 50mL DMSO, 175 DEG C are warming up to；Meanwhile the mixing that 2.5mmol vulcanized sodium is dissolved in 5mL ethanol and 50mL DMSO is molten
In agent；Then, sodium sulfide solution is instilled into source metal solution, 50min is dripped off；175 DEG C of maintenance reaction temperature, react 6h.With third
Ketone avales copper-zinc-tin-sulfur nano particle to come, and centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL third
Ketone, centrifugation, produce the copper-zinc-tin-sulfur nano particle that pure vitamin C wraps up.
Embodiment 8
1.25mmol copper chlorides, 0.625mmol zinc chloride, 0.625mmol stannous chlorides and 1.25mmol vitamin Cs is molten
In 40mL DMSO, 115 DEG C are warming up to；Meanwhile the mixing that 2.5mmol vulcanized sodium is dissolved in 7mL ethanol and 70mL DMSO is molten
In agent；Then, sodium sulfide solution is instilled into source metal solution, 10min is dripped off；110 DEG C of maintenance reaction temperature, react 6h.With third
Ketone avales copper-zinc-tin-sulfur nano particle to come, and centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL third
Ketone, centrifugation, produce the copper-zinc-tin-sulfur nano particle that pure vitamin C wraps up.
Embodiment 9
By 1.25mmol copper acetates, 0.625mmol zinc chloride, 0.625mmol stannic chlorides and 1.25mmol vitamin Cs are dissolved in
In 40mL DMSO, 155 DEG C are warming up to；Meanwhile 2.5mmol thiocarbamides are dissolved in 10mL ethanol and 100mL DMSO mixed solvent
In；Then, thiourea solution is instilled into source metal solution, 15min is dripped off；150 DEG C of maintenance reaction temperature, react 13h.Will with acetone
Copper-zinc-tin-sulfur nano particle, which avales, to be come, and centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL acetone,
Centrifugation, produce the copper-zinc-tin-sulfur nano particle of pure vitamin C parcel.
Embodiment 10
By 1.25mmol copper acetates, 0.625mmol zinc chloride, 0.625mmol stannic chlorides and 1.25mmol vitamin Cs are dissolved in
In 40mL DMSO, 155 DEG C are warming up to；Meanwhile 2.5mmol thiocarbamides are dissolved in 25mL ethanol and 25mL DMSO mixed solvent
In；Then, ethyl mercaptan solution is instilled into source metal solution, 10min is dripped off；110 DEG C of maintenance reaction temperature, react 14h.Use acetone
Copper-zinc-tin-sulfur nano particle is avaled to come, centrifugation obtains black solid.30mL water is added, ultrasonic 10min, adds 30mL third
Ketone, centrifugation, produce the copper-zinc-tin-sulfur nano particle that pure vitamin C wraps up.
Comparative example 1
By 1.25mmol copper acetates, 0.625mmol zinc chloride, 0.625mmol stannic chlorides and 1.25mmol vitamin Cs are dissolved in
In 40mL ethylene glycol solvents, 155 DEG C are warming up to；Meanwhile 2.5mmol vulcanized sodium is dissolved in 55ml ethylene glycol solvents, Qi Tabu
Suddenly with identical in embodiment 1, in the product being prepared, it is impossible to form single structure phase, there is mixture to form (two
Member, ternary mixture), it is impossible to copper-zinc-tin-sulfur nano material is obtained, illustrates that ethylene glycol is not suitable for the preparation method.
Comparative example 2
By 1.25mmol copper acetates, 0.625mmol zinc chloride, 0.625mmol stannic chlorides are dissolved in 40mL DMSO solvents,
Vitamin C is added without, other steps are with identical in embodiment 1, in the product being prepared, it is impossible to form nano material
Good dispersion, observation find to reunite it is obvious, illustrate ascorbic part effect be preparation method success it is indispensable because
Element.
Comparative example 3
Copper acetate is replaced with copper nitrate, zinc nitrate substitutes zinc acetate, and other conditions, step are identical with embodiment 1, system
In standby obtained product, it is impossible to obtain single nano material, observation finds that mixture color mixes, and reaction is unsuccessful.Illustrate this
Preparation method has certain selectivity to reaction raw material, it is impossible to arbitrarily replaces, reason is probably the reaction of different raw material
It is active different, the synchronous reaction of each element can not be realized.
Claims (7)
1. a kind of preparation method of the copper-zinc-tin-sulfur nano particle of vitamin C parcel, it is characterised in that comprise the following steps：
(1) source metal, vitamin C are mixed with dimethyl sulfoxide (DMSO), obtains source metal solution；
Described source metal is metal chloride or metal acetate salt；
(2) sulphur source is mixed with the mixed solvent of proton solvent/dimethyl sulfoxide (DMSO), obtains sulphur source solution；
The volume ratio of the mixed solvent of described proton solvent/dimethyl sulfoxide (DMSO), proton solvent and dimethyl sulfoxide (DMSO) is 1:1~
10；Described sulphur source is vulcanized sodium, ethyl mercaptan or thiocarbamide；
(3) described sulphur source solution is added drop-wise in source metal solution, at 100~180 DEG C after 2~20h of synthesis under normal pressure, through centrifugation
The copper-zinc-tin-sulfur nano particle of isolated vitamin C parcel.
2. the preparation method of the copper-zinc-tin-sulfur nano particle of vitamin C parcel according to claim 1, it is characterised in that
In step (1), in the source metal solution, the concentration in copper source is 10~50mmol/L, and the concentration in zinc source is 5~25mmol/L,
The concentration of tin source is 5~25mmol/L.
3. the preparation method of the copper-zinc-tin-sulfur nano particle of vitamin C parcel according to claim 1 or 2, its feature exist
In in step (1), ascorbic concentration is 10~50mmol/L in the source metal solution.
4. the preparation method of the copper-zinc-tin-sulfur nano particle of vitamin C parcel according to claim 1, it is characterised in that
In step (2), the concentration of the sulphur source solution is 10~50mmol/L.
5. the preparation method of the copper-zinc-tin-sulfur nano particle of the vitamin C parcel according to claim 1 or 4, its feature exist
In in step (2), described proton solvent is methanol, ethanol or water.
6. the preparation method of the copper-zinc-tin-sulfur nano particle of vitamin C parcel according to claim 1, it is characterised in that
In step (3), the volume ratio of the source metal solution and sulphur source solution is 1:1~5.
7. the preparation method of the copper-zinc-tin-sulfur nano particle of the vitamin C parcel according to claim 1 or 6, its feature exist
In in step (3), the time that described sulphur source solution is added drop-wise in source metal solution is 1min~4h.
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| CN103359777A (en) * | 2012-03-29 | 2013-10-23 | 上海交通大学 | Hydrothermal preparation method of CU2ZnSnS4, CU2ZnSnS4 material and application thereof |
| CN103861617A (en) * | 2014-03-28 | 2014-06-18 | 西北师范大学 | Preparation method and application of copper-zinc-tin-sulfur nano-crystalline powder photo-catalyst |
| CN103923515A (en) * | 2014-04-10 | 2014-07-16 | 北京工业大学 | Method for preparing ink capable of being used for preparing Cu2ZnSnS4 solar cell absorption layer film |
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| CN103359777A (en) * | 2012-03-29 | 2013-10-23 | 上海交通大学 | Hydrothermal preparation method of CU2ZnSnS4, CU2ZnSnS4 material and application thereof |
| CN103861617A (en) * | 2014-03-28 | 2014-06-18 | 西北师范大学 | Preparation method and application of copper-zinc-tin-sulfur nano-crystalline powder photo-catalyst |
| CN103923515A (en) * | 2014-04-10 | 2014-07-16 | 北京工业大学 | Method for preparing ink capable of being used for preparing Cu2ZnSnS4 solar cell absorption layer film |
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