CN107572581A - The preparation method of metal sulfide/amine hybrid nano-material and nano metal sulfide material - Google Patents
The preparation method of metal sulfide/amine hybrid nano-material and nano metal sulfide material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method for the method and its corresponding pure nano metal sulfide material that metal sulfide/amine hybrid nano-material is prepared using amine molecule induction back flow reaction method.This method is simple to operate, do not need the reactor of HTHP, cost is cheap, yield is high, and gained metal sulfide/amine hybrid nano-material and its corresponding pure nano metal sulfide material morphology be evenly distributed, superior and be easily enlarged production.The nano material that the present invention obtains can be further applied to lithium-sulfur cell, photocatalysis, electro-catalysis, fire retardant, ultraviolet absorber etc. as good function nano material precursor, be with a wide range of applications and application prospect.
Description
Technical field
It is more particularly to a kind of to be lured using amine molecule the invention belongs to the technical field of the preparation of nano metal sulfide material
Lead back to stream reaction method and prepare the method for metal sulfide/amine hybrid nano-material and its corresponding pure nano metal sulfide material
Preparation method.
Background technology
Metal sulfide/amine hybrid nano-material is because its unique property and various nanostructured are once it is found that cause
People widely pay close attention to.The insertion of amine molecule can not only adjust nano material in metal sulfide/amine hybrid nano-material
Can, and its crystal growing process can be instructed, metal sulfide/amine hybrid nano-material substantial amounts of so far is closed
Further it is widely applied into coming out and causing.Based on the unique property of metal sulfide/amine hybrid nano-material and more
The nanostructured of sample, metal sulfide/amine hybrid nano-material can further prepare corresponding work(as good presoma
Energy property nano material and device, such as annealed processing can obtain simple metal sulfide nano-material, and ion exchange can obtain
Multi-component hybridization nano material, further to improve its performance, widen its application prospect, therefore metal sulfide/amine hybridized nanometer
Material has extensive researching value and application potential.
It is current mainly to be prepared using the method for solvent heat or hydro-thermal reaction for metal sulfide/amine hybrid nano-material,
It is required to carry out using reactor yet with solvent heat or hydro-thermal reaction, equipment is expensive, condition is harsh, low yield, reactant
It is heat transfer and distribution, mass transfer difference etc. are difficult to amplify, is not suitable for industrial mass production, therefore further development metal sulphur
Compound/amine hybrid nano-material preparation method that is simple, inexpensive, being easy to magnanimity has important value and meaning.
The content of the invention
In order to solve it is of the prior art need to use reactor and make it that equipment is expensive, condition is harsh, low yield, reaction
System heat transfer and distribution, mass transfer difference etc. are difficult to amplify, and are not suitable for the technological deficiency of industrial mass production, the present inventor
After having made intensive studies, it was found that a kind of amine molecule simple to operate, high yield induces back flow reaction method to produce metal
The method of sulfide/amine hybrid nano-material.Therefore, the present invention provides following aspect：
<1>A kind of preparation method of metal sulfide/amine hybrid nano-material, methods described comprise the following steps：
Step S1：By metal salt and sulphur source with 1: 0.5-3 mixed in molar ratio, and deionized water is added, and stirred
Dissolving, then add relative to deionized water/small molecule amine mixed liquor that metal salt is every mole metal salt addition 2.5-100L,
To cause the molar concentration of metal salt as 0.01-0.3mol/L, mixed liquor to be mixed, the mixture of acquisition is transferred into band afterwards
Have in the container that length is 30-60cm air set pipes, wherein the metal salt, which is metal ion, is selected from zinc, copper, lead, manganese and cadmium
Any of nitrate, nitrate, chlorate or acetate；
Step S2：Then at ambient pressure, at a temperature of the container being placed in into 180-220 DEG C, the mixing in the container is made
Thing back flow reaction 3-5h, dispersion liquid is obtained after cooling；And
Step S3：It is freeze-dried gained dispersion liquid centrifuge washing and under the conditions of -50 to -80 DEG C and has just obtained metal sulphur
Compound/amine hybrid nano-material.
<2>A kind of preparation method of nano metal sulfide material, methods described comprise the following steps：
Step S1：By metal salt and sulphur source with 1: 0.5-3 mixed in molar ratio, and deionized water is added, and stirred
Dissolving, then add relative to deionized water/small molecule amine mixed liquor that metal salt is every mole metal salt addition 2.5-100L,
And the molar concentration for causing metal salt is 0.01-0.3mol/L, and mixed liquor is mixed, is afterwards transferred to the mixture of acquisition
With length for 30-60cm air set pipes container in, wherein the metal salt be metal ion be selected from zinc, copper, lead, manganese and
Nitrate, nitrate, chlorate or the acetate of any of cadmium；
Step S2：Then at ambient pressure, at a temperature of the container being placed in into 180-220 DEG C, the mixing in the container is made
Thing back flow reaction 3-5h, dispersion liquid is obtained after cooling；
Step S3：It is freeze-dried gained dispersion liquid centrifuge washing and under the conditions of -50 to -80 DEG C and has just obtained metal sulphur
Compound/amine hybrid nano-material；And
Step S4：Under inert atmosphere, at 300-900 DEG C, by the metal sulfide obtained in step S3/amine hybridized nanometer material
Material calcining 2-3h, obtains corresponding pure nano metal sulfide material.
<3>Basis<1>Or<2>Described method, wherein, the metal salt is selected from zinc nitrate hexahydrate, four hydration nitre
Any of sour cadmium, copper acetate dihydrate, lead acetate trihydrate, four acetate hydrate manganese and caddy.
<4>Basis<1>Or<2>Described method, wherein, the sulphur source be selected from thiocarbamide, thioacetamide, vulcanized sodium,
Any of dithizone and sodium diethyldithiocarbamate.
<5>Basis<1>Or<2>Described method, wherein, the small molecule amine be selected from ethylenediamine, diethylenetriamine,
Any of TEPA, cyclohexylamine and n-butylamine.
<6>Basis<1>Or<2>Described method, wherein, the metal salt is zinc nitrate hexahydrate, and the sulphur source is sulphur
Urea, and the small molecule amine is diethylenetriamine.
<7>Basis<1>Or<2>Described method, wherein, deionized water described in the step S1/small molecule amine mixing
The volume of liquid small molecular amine is 6-12 times of water volume.
<8>Basis<1>Or<2>Described method, wherein the nano material has selected from nanobelt, nano wire, nanometer
Any nanostructure types in piece, nanosphere, nanometer blocks and rod mixing nanostructured.
<9>Basis<1>Or<2>The stirring and mixing in described method, wherein step S1 are in ultrasonication
Lower progress.
<10>Basis<1>Or<2>Described method, gained dispersion liquid centrifuge washing being entered wherein described in step S3
At least 3 times centrifugation washings of row.
The present invention presents a kind of new induces back flow reaction method to produce metal sulfide/amine hydridization using amine molecule
Nano material (especially zinc sulphide-diethylenetriamine hybrid nano-material), this method is simple to operate (not to need HTHP
Reactor), cost is cheap, yield is high, gained metal sulfide/amine hybrid nano-material and its corresponding pure metal sulfide are received
Rice material morphology is evenly distributed, is superior and be easily enlarged production；And corresponding metal sulfide/amine hybrid nano-material
Lithium-sulfur cell, photocatalysis, electro-catalysis, fire retardant, purple can be further applied to as good function nano material precursor
Outer absorbent etc., is with a wide range of applications and application prospect.
Brief description of the drawings
Fig. 1 is the photo of the SEM of zinc sulphide-diethylenetriamine hybridized nanometer piece of the present invention；
Fig. 2 is the photo of the transmission electron microscope of zinc sulphide-diethylenetriamine hybridized nanometer piece of the present invention；
Fig. 3 is the photo of the AFM of zinc sulphide-diethylenetriamine hybridized nanometer piece of the present invention；
Fig. 4 is the picture of the powder x-ray diffraction of zinc sulphide-diethylenetriamine hybridized nanometer piece of the present invention；
Fig. 5 is the photo of the transmission electron microscope of the zinc sulfide nano piece of the present invention；
Fig. 6 is the photo of the high resolution transmission electron microscopy of the zinc sulfide nano piece of the present invention；
Fig. 7 is the photo of the AFM of the zinc sulfide nano piece of the present invention；
Fig. 8 is zinc sulphide-diethylenetriamine hybridized nanometer piece thermogravimetric analysis image of the present invention；
Fig. 9 is the picture of the powder x-ray diffraction of the zinc sulfide nano piece of the present invention；
Figure 10 is zinc sulphide-diethylenetriamine hybridized nanometer piece crystal structure model of the present invention；
Figure 11 is zinc sulphide-diethylenetriamine hybridized nanometer piece of the new amine molecule back flow reaction method amplification production of the present invention
And solvent thermal reaction products therefrom contrast scans figure under corresponding conditionses；
Figure 12 is the transmission electron microscope photo of superfine cadmium sulfide (CdS) nano wire of the present invention；
Figure 13 is the optical photograph of the ultra-fine CdS nano wires of the present invention；
Figure 14 is the X-ray diffraction photo of the ultra-fine CdS nano wires of the present invention；
Figure 15 is the Cu of the present invention31S16The photo of nanosphere transmission electron microscopy；
Figure 16 is the Cu of the present invention31S16The electron scanning micrograph of nanosphere；
Figure 17 is the Cu of the present invention31S16The X-ray diffraction photo of nanosphere
Figure 18 is the electron scanning micrograph of the PbS nanometer blocks of the present invention；
Figure 19 is the X-ray diffraction photo of the PbS nanometer blocks of the present invention
Figure 20 is the Mn of the present invention2The photo of the transmission electron microscope of S nano material；
Figure 21 is the Mn of the present invention2The X-ray diffraction photo of S nano material.
The SEM of Zesiss Supra 40 (SEM), JEOL-2010 transmission electron microscopes is respectively adopted
(TEM), JEM-ARM 200F types high resolution electron microscope, Veeco DI Nano-scope MultiMode V-type atomic forces
Microscope (AFM) Philips X ' Pert PRO SUPER types x-ray diffractometers (XRD), Perkin Elmer Diamond types
Thermogravimetric analyzer characterizes to products therefrom.
Embodiment
The invention provides a kind of new amine molecule induction back flow reaction method to produce metal sulfide/amine hybridized nanometer material
Expect the method for (especially zinc sulphide-diethylenetriamine hybrid nano-material) and its corresponding pure nano metal sulfide structural wood
Material.The back flow reaction method of new amine molecule induction of the present invention need not use the operation letter of the reactor of HTHP
List, cost is cheap, yield is high, gained metal sulfide/amine hybrid nano-material and its corresponding pure nano metal sulfide knot
Structure material morphology is evenly distributed, superior and be easily enlarged production, is with a wide range of applications and application value.
It is current main using the preparation of the method for solvent heat or hydro-thermal reaction for metal sulfide/amine hybrid nano-material.
Hydro-thermal or solvent thermal reaction refer in enclosed system such as autoclave, in certain temperature (100-1000 DEG C) and pressure (1-100MPa)
Under the conditions of, a kind of synthetic method that original stock is reacted.It is special closing, the reaction environment of high temperature high voltage resistant determine,
Hydro-thermal or solvent thermal reaction, more expensive equipment requirement, the container wall layer thickness of high pressure resistant super thick determine its poor heat transfer
Property.For the synthesis of metal sulfide/amine hybrid nano-material, conventional synthetic method is hydro-thermal or solvent thermal reaction, for
Under laboratory environment, micro or a small amount of synthetic reaction, reactor belongs to conveniently reactor, less volumetric mass transfer,
Heat transfer influence is smaller, but it is more difficult to be limited to the mass transfer of difference, the further expanding production of heat transfer.
Therefore, it is of the invention be to provide a kind of new induce back flow reaction method using amine molecule to produce metal vulcanization
The method of thing/amine hybrid nano-material and its corresponding simple metal sulfide nano structural material, methods described comprise the following steps：
Step S1：By metal salt and sulphur source with 1: 0.5-3, be preferably in a proportion of 1: 1 mixed in molar ratio, and add go from
Sub- water, and stirring and dissolving, it is to add 2.5-100L, preferably 3-10L, optimal per mole metal salt then to add relative to metal salt
Select 5-8L deionized water/small molecule amine mixed liquor (being calculated with mixed liquor cumulative volume), using cause the molar concentration of metal salt as
0.01-0.3mol/L, preferably 0.1-0.3mol/L, by mixed liquor ultrasonic mixing, the mixture of acquisition is transferred to band afterwards
Have in the container that length is 30-60cm air set pipes, wherein the metal salt, which is metal ion, is selected from zinc, copper, lead, manganese and cadmium
Any of nitrate, nitrate, chlorate or acetate；
Step S2：Then at ambient pressure, the container is placed in 180-220 DEG C, preferably at 185-210 DEG C, most preferably existed
At a temperature of 200 DEG C, make the mixture back flow reaction 3-5h in the container, preferably 4-4.5 hours, be subsequently cooled to room temperature, with
Obtain dispersion liquid；
Step S3：It is freeze-dried just by gained dispersion liquid centrifuge washing and at -50 to -80 DEG C of temperature, preferably 60-80 DEG C
Metal sulfide/amine hybrid nano-material is obtained；
Step S4：Under inert atmosphere, at 300-900 DEG C, preferably at 300-600 DEG C, most preferably at 400 DEG C, by step S3
In obtained metal sulfide/amine hybrid nano-material annealing (that is, calcine) 2-3h, obtain corresponding pure metal sulfide
Nano material.
Can be seen that from preparation process above can obtain metal sulfide/amine hybridized nanometer material by step S1-S3
Material, and by step S4 small molecule organic amine can be caused to locate again the metal sulfide obtained/amine hybrid nano-material
Volatilized during reason, so as to obtain corresponding pure nano metal sulfide material.
Photo, electron scanning micrograph and the original of transmission electron microscopy appeared in the accompanying drawing 1-21 of the present invention
The preparation method that the photo of sub- force microscope can be seen that the present invention obtains metal sulfide/amine hybrid nano-material and its phase
Ying Chun metal sulfide nano-structure material can be clearly shown as nano wire, nanometer sheet, nanosphere, nanometer blocks or rod
Mix nanostructured, etc..
In the present invention, " pure " in wording " corresponding simple metal sulfide nano structural material " refers to organic molecule
Nano metal sulfide material after volatilization is removed.
In the present invention, the use of with length is that 30-60cm air set pipes reduce moisture rapid evaporation.
In the present invention, the metal salt is selected from zinc nitrate hexahydrate, four nitric hydrate cadmiums, copper acetate dihydrate, three water
Close any of lead acetate, four acetate hydrate manganese and caddy, most preferably zinc nitrate hexahydrate.
In the present invention, the sulphur source is to be selected from thiocarbamide, thioacetamide, vulcanized sodium, dithizone and diethyl-dithio
Any of carbamic acid sodium, most preferably thiocarbamide.
In the present invention, the small molecule amine is selected from ethylenediamine, diethylenetriamine, TEPA, cyclohexylamine and just
Any of butylamine, most preferably diethylenetriamine.
In the present invention, the volume of the deionized water/small molecule amine mixed liquor small molecular amine is the 6-12 of water volume
Times.
In the preparation process in accordance with the present invention, do not complete to react using the reactor of high pressure-temperature is needed.In fact,
The present inventor by with the correlation method using reactor relatively after learn, the use of high-temperature high-pressure reaction kettle is not improved this
The conversion ratio of reaction is invented, is conversely to have reduced to 56.2% conversion ratio (referring to embodiment 2 once from 85.0% conversion ratio
Result), this explanation inventor proposed new amine molecule induction back flow reaction method can obtain higher conversion ratio.And
By SEM photograph it is recognised that the hybridized nanometer piece and solvent thermal reaction method that will be obtained using amine molecule induction back flow reaction method
Obtain hybridized nanometer piece to compare, there is pattern evenly, the sulfide nanometer sheet obtained by annealing is kept well
Original hybridized nanometer chip architecture (referring to Figure of description 11).This further illustrates amine molecule induction back flow reaction method is excellent
Different heat conductivity and it is easily enlarged productivity on the basis of good pattern is maintained.
The present invention proposes a kind of new amine molecule in metal sulfide/amine hybrid nano-material synthesis field first and lured
Stream reaction method is led back to synthesize metal sulfide/amine hybrid nano-material and its corresponding simple metal sulfide nano structural material,
This method is simple to operate, cost is cheap, yield is high, gained metal sulfide/amine hybrid nano-material and its corresponding simple metal sulphur
Compound nano structural material topographic profile is uniform, superior and be easily enlarged production, be with a wide range of applications with should
With value.
In one embodiment of the invention, the metal sulfide/amine hybrid nano-material for preparing of the invention is
Zinc sulphide-diethylenetriamine hybrid nano-material and its corresponding pure zinc sulphide nano structural material.Specifically, the zinc sulphide-
The preparation method of diethylenetriamine hybrid nano-material and its corresponding pure zinc sulphide nano structural material comprises the following steps：
Step S1：Appropriate zinc nitrate hexahydrate and thiocarbamide are weighed, adds in 250ml beakers, adds going for 120-220ml
Ionized water/diethylenetriamine mixed liquor, ultrasound, stirring are then transferred into 250ml round-bottomed flasks and connected to being completely dissolved
Upper length is 30-60cm air set pipes；
Step S2：At ambient pressure, the round-bottomed flask is placed in back flow reaction 3-5h under the conditions of 180-220 DEG C of oil bath, so
After naturally cool to room temperature, obtain dispersion liquid；
Step S3：Dispersion liquid centrifuge washing obtained by step S2 and freeze-drying zinc sulphide-divinyl three has just been obtained into
Amine hybrid nano-material；
Step S4：The zinc sulphide that step S3 is obtained-diethylenetriamine hybrid nano-material is made annealing treatment, i.e.,：It is lazy
Property atmosphere under, 300-900 DEG C of calcining 2-3h can obtain corresponding pure zinc sulfide nano-material in tube furnace.
In the method for the present invention for preparing zinc sulphide-diethylenetriamine hybrid nano-material, six water in step S1
Nitric acid Zn content 2-60mmol is closed, and the mole that thiocarbamide adds in step S1 is identical with zinc nitrate hexahydrate, scope is also 2-
60mmol。
In the method for the present invention for preparing zinc sulphide-diethylenetriamine hybrid nano-material, step S1 intermediate ions
The volume of diethylenetriamine is 8-12 times of water volume in water/diethylenetriamine mixed liquor.
By SEM, TEM, AFM photo it is recognised that the zinc sulphide-two of the embodiment acquisition in the inventive method
Ethene triamine hybridized nanometer piece has uniform pattern, and specific length range is 1-4 μm, and average value is about 2.4 μm, thickness range
24-27nm, average value is about 25nm, 0.5-2 μm of width range, and average value is about 0.96 μm.Zinc sulphide-divinyl three of gained
Amine hybridized nanometer piece passes through the zinc sulfide nano piece that annealing obtains, and it maintains original nanometer chip architecture well, and
And because the zinc sulfide nano piece thickness obtained by the volatilization of organic component has been reduced, average thickness is about 18nm.
With reference to earlier data and pertinent literature, inventor thinks zinc sulphide-diethylenetriamine hydridization prepared by the present invention
Nanometer sheet is organic-inorganic hybrid nano material, and overall is in sandwich structure feature, i.e. two-dimentional monolayer arranged in parallel without
It is closely joined together between machine zinc sulphide by diethylenetriamine, it is overall that orthorhombic structure (as shown in Figure 10) is presented.
In the case of being not bound by any theory, inventor speculates, the presence of water promotes zinc salt and diethylenetriamine
Dissociation, that is, forming the diethylenetriamine of one positive charge of divalent zinc ion and band, (diethylenetriamine represents with DETA, a positive electricity
The diethylenetriamine of lotus is DETA+), and hydroxyl monovalence anion is accordingly generated, presence hydroxy can promote divalent zinc
Ion forms two-dimensional layer Zn (OH)2-x(NO3)x mH2O composite material precursor templates, and Zn (OH)2-x(NO3)x mH2O is answered
Condensation material presoma template can ultimately result in generation as the two-dimensional slice template of zinc sulphide-diethylenetriamine alternating growth
Two-dimensional sheet zinc sulphide-diethylenetriamine hybridized nanometer piece.
Embodiment
It is further described, but does not limit to below in conjunction with accompanying drawing, using embodiment to technical scheme
These embodiments.It is every that technical solution of the present invention is entered in the case where not departing from the spirit and scope of technical solution of the present invention
Capable modification or equivalent substitution all should be considered as covering in protection scope of the present invention.
Embodiment 1：
Zinc sulphide-diethylenetriamine hydridization and pure zinc sulphide nanometer piece preparation method
7.5mmol zinc nitrate hexahydrate (2.23g) and the thiocarbamide (0.57g) of equimolar amounts are added into 250ml beakers,
Then to 22ml deionized waters are added in reaction vessel, it is stirred by ultrasonic to all solutes and fully dissolves.
Then 198ml diethylenetriamines are added into solution, continue ultrasound, stirring.Then, gained dispersion liquid is transferred to
In 250ml round-bottomed flasks, 50cm air set pipe is connected, sustained response 4h under the conditions of 220 DEG C of oil bath heatings is naturally cold afterwards
But room temperature is arrived.The dispersion liquid obtained centrifugation washing is handled three times, rotating speed 3000rpm, time 3min.Finally, gained is produced
- 80 DEG C of freeze-drying process of thing, you can obtain zinc sulphide-diethylenetriamine hybridized nanometer piece.Zinc sulphide-the divinyl that will be obtained
In an inert atmosphere, 400 DEG C of annealing 2-3h can obtain corresponding pure zinc sulphide and receive triamine hybridized nanometer piece in tube furnace
Rice piece.
By SEM, TEM, AFM photo it is recognised that zinc sulphide-diethylenetriamine hybridized nanometer piece has uniform shape
Looks, specific length is about 2.4 μm, thickness is about 25nm, width is about 0.96 μm, the zinc sulfide nano obtained by annealing
Piece maintains original nanometer chip architecture well.Due to the zinc sulfide nano piece thickness obtained by the volatilization of organic component
Reduce, about 18nm.Corresponding XRD, it further demonstrate zinc sulphide-diethylenetriamine hybrid nanostructure (and document
Advanced Materials, 2002, volume 14,296-300 pages, Small, 2005, volume 1,320-325 pages matched),
And it is ultrapure buergerite phase structure to make annealing treatment obtained zinc sulfide nano piece.
Embodiment 2：
Zinc sulphide-diethylenetriamine hydridization and pure zinc sulphide nanometer sheet expand preparation method
120mmol zinc nitrate hexahydrate (35.68g) and the thiocarbamide of equimolar amounts are added into 500ml beakers
(9.12g), then to 45ml deionized waters are added in reaction vessel, it is stirred by ultrasonic and 360ml divinyls three is added into solution
Amine, continue ultrasound, stirring to all solutes is fully dissolved.Then, gained dispersion liquid is transferred in 500ml round-bottomed flasks, should
Round-bottomed flask is connected with 50cm air set pipe, sustained response 4h under the conditions of 220 DEG C of oil bath heatings, naturally cools to room afterwards
Temperature.The dispersion liquid obtained centrifugation washing is handled three times, rotating speed 3000rpm, time 3min.Finally, by -50 DEG C of products therefrom
Freeze-drying process under temperature conditionss, you can obtain zinc sulphide-diethylenetriamine hybridized nanometer piece.Zinc sulphide-diethylenetriamine
Hybridized nanometer tablet quality is 15.2g, and corresponding conversion ratio is 85.0%.If change round-bottomed flask into 500ml reactors, other conditions
The identical product quality that obtains is 10.0g, and corresponding conversion ratio is 56.2%, illustrates new amine molecule induction proposed by the invention
Back flow reaction method has higher conversion ratio.
By SEM photograph it is recognised that inducing zinc sulphide-divinyl three of back flow reaction method expanding production using amine molecule
For amine hybridized nanometer piece compared to solvent thermal reaction with pattern evenly, the zinc sulfide nano piece obtained by annealing is fine
Ground maintains original nanometer chip architecture, further illustrates the excellent heat conductivity of amine molecule induction back flow reaction method and is tieing up
Hold and be easily enlarged productivity on the basis of good pattern.
Embodiment 3
Ultra-fine CdS nanowire preparation methods
7.5mmol four nitric hydrate cadmiums (2.31g) and the thiocarbamide (0.57g) of equimolar amounts are added into 250ml beakers,
Then to 20ml deionized waters are added in reaction vessel, it is stirred by ultrasonic to all solutes and fully dissolves.
Then 200ml diethylenetriamines are added into solution, continue ultrasound, stirring.Then, gained dispersion liquid is transferred to
In 250ml round-bottomed flasks, 50cm air set pipe is connected, sustained response 4h under the conditions of 220 DEG C of oil bath heatings is naturally cold afterwards
But room temperature is arrived.The dispersion liquid obtained centrifugation washing is handled three times, then freezed products therefrom under -80 DEG C of temperature conditionss
Drying process, you can obtain ultra-fine CdS nano wires.
It is specific long by TEM, optical photograph it is recognised that ultra-fine CdS nano wires have uniform pattern, big yield
It is about 10nm to spend for 500nm-2 μm, diameter, and has good dispersiveness.Corresponding XRD, it further demonstrate ultra-fine CdS
Nano wire is hexagonal phase structure.
Embodiment 4：
Cu31S16Nanosphere preparation method
Present embodiment as different from Example 5, corresponding four nitric hydrates cadmium is changed to a hydration of equimolar amounts
Copper acetate (1.5g).
It is monocline crystalline phase by TEM, SEM, XRD photo it is recognised that obtained product has uniform nanometer spherical structure
Cu31S16Nanometer spherical structure.
Embodiment 5：
PbS nanometer blocks preparation methods
Present embodiment as different from Example 5, corresponding four nitric hydrates cadmium is changed to three hydrations of equimolar amounts
Lead acetate (2.44g).
By SEM, XRD photo it is recognised that obtained product has uniform nanometer block structure, product is Emission in Cubic
PbS nanometer block structures.
Embodiment 6：
Mn2S preparation method of nano material
Present embodiment as different from Example 5, corresponding four nitric hydrates cadmium is changed to four hydrations of equimolar amounts
Manganese acetate (1.84g).
By SEM, XRD photo it is recognised that obtained product is ball, rod mixing nanostructured, final product is cube
Phase Mn2S nano materials.
Embodiment 7：
Present embodiment as different from Example 5, corresponding four nitric hydrates cadmium is changed to the caddy of equimolar amounts
(1.37g)。
Embodiment 8
Present embodiment as different from Example 5, corresponding thiocarbamide is changed to the dithizone of equimolar amounts.
Embodiment 9
Present embodiment as different from Example 5, corresponding diethylenetriamine is changed to four ethene five of equimolar amounts
Amine.
Industrial applicability
The metal sulfide that the present invention obtains/amine hybrid nano-material and its corresponding pure nano metal sulfide material
Material, topographic profile is uniform, it is superior and easily amplification prepare, be with a wide range of applications and application potential.Especially,
Metal sulfide/amine hybrid nano-material that the present invention is obtained can enter one as good function nano material precursor
Step is applied in lithium-sulfur cell, photocatalysis, electro-catalysis, fire retardant, ultraviolet absorber etc., is with a wide range of applications with answering
Use prospect.
Claims (10)
1. a kind of preparation method of metal sulfide/amine hybrid nano-material, methods described comprise the following steps：
Step S1：By metal salt and sulphur source with 1: 0.5-3 mixed in molar ratio, and deionized water is added, and stirring and dissolving,
Then add relative to deionized water/small molecule amine mixed liquor that metal salt is every mole metal salt addition 2.5-100L, so that
The molar concentration for obtaining metal salt is 0.01-0.3mol/L, and mixed liquor is mixed, and the mixture of acquisition is transferred to length afterwards
Spend in the container for 30-60cm air set pipes, wherein the metal salt is metal ion in zinc, copper, lead, manganese and cadmium
Any nitrate, nitrate, chlorate or acetate；
Step S2：Then at ambient pressure, at a temperature of the container being placed in into 180-220 DEG C, return the mixture in the container
Stream reaction 3-5h, dispersion liquid is obtained after cooling；And
Step S3：It is freeze-dried gained dispersion liquid centrifuge washing and under the conditions of -50 to -80 DEG C and has just obtained metal vulcanization
Thing/amine hybrid nano-material.
2. a kind of preparation method of nano metal sulfide material, methods described comprise the following steps：
Step S1：By metal salt and sulphur source with 1: 0.5-3 mixed in molar ratio, and deionized water is added, and stirring and dissolving,
Then add relative to deionized water/small molecule amine mixed liquor that metal salt is every mole metal salt addition 2.5-100L, and
So that the molar concentration of metal salt is 0.01-0.3mol/L, mixed liquor is mixed, the mixture of acquisition is transferred to carried afterwards
Length is in the container of 30-60cm air set pipes, wherein the metal salt is metal ion in zinc, copper, lead, manganese and cadmium
Any nitrate, nitrate, chlorate or acetate；
Step S2：Then at ambient pressure, at a temperature of the container being placed in into 180-220 DEG C, return the mixture in the container
Stream reaction 3-5h, dispersion liquid is obtained after cooling；
Step S3：It is freeze-dried gained dispersion liquid centrifuge washing and under the conditions of -50 to -80 DEG C and has just obtained metal vulcanization
Thing/amine hybrid nano-material；And
Step S4：Under inert atmosphere, at 300-900 DEG C, the metal sulfide obtained in step S3/amine hybrid nano-material is forged
2-3h is burnt, obtains corresponding pure nano metal sulfide material.
3. method according to claim 1 or 2, wherein, the metal salt is selected from zinc nitrate hexahydrate, four nitric hydrates
Any of cadmium, copper acetate dihydrate, lead acetate trihydrate, four acetate hydrate manganese and caddy.
4. method according to claim 1 or 2, wherein, the sulphur source is selected from thiocarbamide, thioacetamide, vulcanized sodium, double
Any of sulphur hydrazone and sodium diethyldithiocarbamate.
5. method according to claim 1 or 2, wherein, the small molecule amine is selected from ethylenediamine, diethylenetriamine, four
Any of the amine of ethene five, cyclohexylamine and n-butylamine.
6. method according to claim 1 or 2, wherein, the metal salt is zinc nitrate hexahydrate, and the sulphur source is sulphur
Urea, and the small molecule amine is diethylenetriamine.
7. method according to claim 1 or 2, wherein, deionized water/small molecule amine mixed liquor described in the step S1
The volume of small molecular amine is 6-12 times of water volume.
8. method according to claim 1 or 2, wherein the nano material has selected from nanobelt, nano wire, nanometer
Any nanostructure types in piece, nanosphere, nanometer blocks and rod mixing nanostructured.
9. the stirring and mixing in method according to claim 1 or 2, wherein step S1 are under ultrasonication
Carry out.
10. method according to claim 1 or 2, gained dispersion liquid centrifuge washing is carried out wherein described in step S3
At least 3 times centrifugation washings.
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