CN105819490B - Method for preparing different-morphology and self-assembly Cu2S nanometer materials - Google Patents
Method for preparing different-morphology and self-assembly Cu2S nanometer materials Download PDFInfo
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- CN105819490B CN105819490B CN201610163670.4A CN201610163670A CN105819490B CN 105819490 B CN105819490 B CN 105819490B CN 201610163670 A CN201610163670 A CN 201610163670A CN 105819490 B CN105819490 B CN 105819490B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a method for preparing different-morphology and self-assembly Cu2S nanometer materials, and belongs to the field of semiconductor nanometer material preparing.The method includes the following steps that 1, biphenyl mercaptan, an acid-binding agent and an organic solvent are mixed to be even, cuprous chloride is added under the protection of nitrogen, and the mixture is reacted for 2 h to 6 h at the temperature of 10 DEG C to 30 DEG C; 2, a Cu2S precursor is prepared; 3, the different-morphology and self-assembly Cu2S nanometer materials are prepared.According to the preparing method, the synthesis technology is controlled, the Cu2S precursor which is of a highly-ordered layered structure is synthesized, then the difference of the dissociation degree of the layered structure of the precursor under different conditions is adopted, and therefore the different-morphology and self-assembly Cu2S nanometer materials are prepared.Compared with an existing preparing technology of Cu2S nanometer materials, by means of the preparing method, the morphology of the product can be better controlled, and the obtained product is good in dispersibility, and has the good application prospects in the solar energy field, the lithium ion battery field, the photocatalysis field and the like.
Description
Technical field
The invention belongs to the preparation field of sulfide compound semiconductor nano material, and in particular to a kind of different-shape is from group
Dress Cu2The preparation method of S nano materials.
Background technology
Cuprous sulfide (Cu2S) be common indirect band gap P-type semiconductor in one kind, its energy gap be 1.2eV,
Exist in a large number in the form of vitreous copper in nature.Cu2S it is nanocrystalline due to its quantum size effect show uniqueness physics and
Chemical property, has a wide range of applications in fields such as energy storage, photoelectric device, plasma resonances.Development is easy, can
Control, pervasive, eco-friendly Syntheses method are prepared with realizing the nano material with specific composition, size, pattern, and
Further function nano crystalline substance assembly is assembled into build nano-device by controllable, it is extensive for developing nano material
Using having great importance.
Investigation of materials personnel both domestic and external are in Cu2Substantial amounts of research is carried out simultaneously in S nanocrystalline controllable standby and assembling
Some impressive progresses are achieved, such as Donghua University Hu Junqing seminars have synthesized list in water phase by strict control reaction condition
Dispersion Cu2S is nanocrystalline, subsequently the method by removing some ligands stabilizer, successfully assembles high length-diameter ratio one-dimensional and two
Dimension structure.Fujian Wu Gousuochen tinkling of pieces of jade seminar of the Chinese Academy of Sciences is prepared for Cu by thermally decomposing alkyl sulfide alkoxide2S nanometer plates and its assembling
Body.However, research employing at present is mostly solution system, preparation process is cumbersome, and the response time is long, different in same system
It is little that pattern is particularly the controlled standby research report of the monodimension nanometer materials such as nanometer rods, nano wire.Therefore, in order to preferably control
The structure and microscopic appearance of product processed, explores a kind of universality, environmental friendliness, more controlled many pattern self assembly Cu2S nanometers
Crystal preparation method becomes the problem of urgent need to resolve.
The content of the invention
It is an object of the invention to overcome Cu in the presence of prior art2On S nanomaterial assembly bodily form looks are uncontrollable
State deficiency, there is provided a kind of different-shape self assembly Cu2The preparation method of S nano materials, the preparation method adopts routine techniquess handss
Duan Zuhe, it is with low cost with simple to operate, it is easy to accomplish the characteristics of, promote to realize by the collaboration between processing step
Different-shape self assembly Cu2S nano materials prepare purpose, prepared Cu2S Nanoscale assemblies have excellent dispersibility and can
The pattern of control, has a good application prospect in fields such as solar energy, lithium ion battery and photocatalysis.
In order to realize foregoing invention purpose, the invention provides technical scheme below：
A kind of different-shape self assembly Cu2The preparation method of S nano materials, comprises the following steps：
(1) by biphenyl mercaptan, acid binding agent and organic solvent mix homogeneously, Cu-lyt. is added under nitrogen protection, in 10
～30 DEG C of 2～6h of reaction；
(2) reacting liquid filtering for preparing step (1), gained filter cake absolute ethanol washing subsequently does filter cake vacuum
It is dry to obtain Cu2S presomas；
(3) Cu for preparing step (2)2S presomas are calcined under vacuum or atmosphere of inert gases, when being in
During vacuum, calcining heat is 200～240 DEG C；When in atmosphere of inert gases, calcining heat is 200～220 DEG C, is obtained
To different-shape self assembly Cu2S nano materials.
Above-mentioned preparation method synthesizes first the Cu in high ordered lamellar structure by controlling synthesis technique2S presomas,
Then presoma is utilized in the diversity of different experimental conditions Layered structure dissociation degree, so as to prepare different-shape from group
Dress Cu2S nano materials.The Cu in above-mentioned steps (3) calcination process2The high ordered lamellar structure of S presomas slowly dissociates, and C-S keys break
Schizogenesis is into Cu2S.Detailed process is：Under vacuum during 200～220 DEG C of calcinings, reaction rate is relatively slow, predecessor stratiform
Structure is easily controllable, thus the Cu for being formed2S is nanocrystalline to be only capable of free diffusing growth, the nanocrystalline succession precursor of generation in layer
The order of stratiform, is self-assembled into Cu2S nano wire assemblies.When being warming up to 240 DEG C, reaction rate is accelerated, presoma stratiform
Mesomorphic phase structure becomes to be difficult controlled, and local layer structure may collapse, thus Cu2S is nanocrystalline raw in partial layer inner structure
While long, interlayer also has slow diffusion, and the iris action due to being limited to long alkyl layer, this speed of growth compares layer
It is interior more slowly, so as to result in Cu2The generation of S nanometer sheet；Under atmosphere of inert gases, Cu when 200 DEG C of calcinings2S nano wire groups
The formation mechenism of dress body is identical with 200～220 DEG C of calcinings under vacuum, but in liter high-temperature, its reaction rate is compared very
Empty atmosphere faster when such as rising to 220 DEG C of higher temperature, can generate Cu at the same temperature2S nanometer plate assemblies.This explanation
Presoma stratiform mesomorphic phase structure compares that the lower 240 DEG C of calcinings of vacuum are more uncontrolled, and now stratiform mesomorphic phase structure is further
Collapse, while the arrangement of interlayer direction alkyl chain also more " loose ", eventually forms nanometer plate assembly.
Preferably, biphenyl mercaptan is represented with formula (1) in above-mentioned steps (1)：
Interval base is hexyloxy in said structure, and tail chain is butoxy, hexyloxy, octyloxy, decyloxy or dodecane oxygen
Base (n=4,6,8,10,12).When reaction system uses biphenyl mercaptan as sulphur source, due to biphenyl mercaptan biphenyl structural compared with
The chain hydrocarbon structure of aliphatic mercaptan has bigger stiffness, and the high ordered lamellar structure that it is generated is difficult in calcining
Subside such that it is able to prepare the cuprous sulfide nano material of self assembly.
Preferably, acid binding agent is one or more in three second ammoniums, ammonium acetate and pyridine in above-mentioned steps (1), using tiing up
Sour agent is conducive to the H generated during quick absorbing reaction2S gases, while environmental pollution is reduced Cu is promoted2S presomas
Formed.
Preferably, the mol ratio of biphenyl mercaptan and Cu-lyt. is 1: 1～1.2: 1 in above-mentioned steps (1).Proportioning raw materials exist
Can guarantee that synthetic reaction is fully carried out in the molar ratio range, while and avoiding unnecessary side reaction from occurring.
Preferably, organic solvent is one or more in toluene, tetrahydrofuran and dichloromethane in above-mentioned steps (1),
Above-mentioned organic solvent can make copper ion solvation, meanwhile, also due to the organic solvent is difficult to provide proton in itself, with very strong
Solvability.Most preferably, from toluene as solvent.
Preferably, use relative to 1～3 times of body of reactant liquor during absolute ethanol washing filter cake in above-mentioned steps (2)
Long-pending dehydrated alcohol is washed.In Cu2In the preparation process of S presomas, easy remained unreacted is completely former in reactant liquor
Material, additive and solvent, these impurity can have a negative impact to follow-up calcine technology.Using in above-mentioned volume range
Dehydrated alcohol is washed to filter cake, can fully remove residual impurity, improves the Cu for preparing2The purity of S nano materials.
Preferably, the baking temperature of filter cake is 80～100 DEG C in above-mentioned steps (2), and drying time is 4～6h.
Preferably, noble gases are helium, neon or argon in above-mentioned steps (3).
Preferably, calcination time is 1～3h in above-mentioned steps (3).When calcination time is less than 1h, due to the response time too
Short, reaction not enough completely, causes Cu2S nano materials are mainly in granular form, it is impossible to form self-assembled structures.Calcination time is more than
During 3h, because the response time is long, the nanostructured of generation is further heated and causes recrystallization so that original structure quilt
Destruction.
Compared with prior art, beneficial effects of the present invention：
1. the present invention is from simple, easily controlled synthesis Cu2S is nanocrystalline to set out, with the Cu in high ordered lamellar structure for preparing2S
Presoma is raw material, by simple solvent-free method for pyrolysis, using dissociation degree of the presoma under different pyrolytical conditions, and can
Different-shape self assembly Cu is prepared in control2S nano materials.
2. the Cu that the present invention is prepared2S nano materials, product dispersibility is very good, morphology controllable.By simple
Solwution method obtains Cu2S presomas, subsequently just can prepare different-shape self assembly Cu by the regulation and control of pyrolytical condition2S nanometer materials
Material, cycle is short, it is easy to amplificationization is suitable to industrialization.
3. the different-shape self assembly Cu that prepared by the present invention2S nano materials, in solar energy, lithium ion battery and photocatalysis
Have a good application prospect Deng field.
Description of the drawings
Fig. 1 is different-shape self assembly Cu of the present invention2S nano materials prepare schematic diagram.
Fig. 2 is Cu prepared by the embodiment of the present invention 12The SAXS figures of S presomas.
Fig. 3 is self assembly Cu prepared by the embodiment of the present invention 12The XRD figure of S nano wires.
Fig. 4 is self assembly Cu prepared by the embodiment of the present invention 12The TEM figures of S nano wires.
Fig. 5 is self assembly Cu prepared by the embodiment of the present invention 22The TEM figures of S nanometer sheet.
Fig. 6 is self assembly Cu prepared by the embodiment of the present invention 32The TEM figures of S nanometer plates.
Fig. 7 is Cu prepared by comparative example of the present invention 12The TEM figures of S nanometer plates.
Fig. 8 is Cu prepared by comparative example of the present invention 22The TEM figures of S nanometer plates
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
Scope for above-mentioned theme of the invention is only limitted to below example, and all technologies realized based on present invention belong to this
The scope of invention.
Embodiment 1
As shown in Figure 1 technique prepares self assembly Cu2S nano wires, by 20mmol 4- hexyloxy -4 '-(10- sulfydryl last of the ten Heavenly stems oxygen
Base) biphenyl and the second ammoniums of 20mmol tri- added in 60ml toluene, stirs 20min, and being allowed to be uniformly dispersed add after nitrogen protection is lower
20mmolCuCl, at 20 DEG C 6h is reacted.Room temperature is cooled to after the completion of reaction, crude product is filtered to obtain, crude product is clear with dehydrated alcohol
Wash, the sample for obtaining is vacuum dried into 6h at 80 DEG C, obtain yellow Cu2S presomas.The aforementioned Cu of precise 0.5g2S presomas, so
Afterwards 1h is calcined under 200 DEG C of vacuums, finally give black self assembly Cu2S nano wires.
The Cu that will be prepared2S presomas and self assembly Cu2S nano wires carry out X-ray small angle and Wide angle X-ray diffraction analytical table
Levy, as a result distinguish as shown in Figure 2,3.Self assembly Cu2S nano wires carry out transmission electron microscope (TEM) sign, as a result such as Fig. 4
It is shown.
Embodiment 2
As shown in Figure 1 technique prepares self assembly Cu2S nanometer sheet, by 20mmol 4- hexyloxy -4 '-(10- sulfydryl last of the ten Heavenly stems oxygen
Base) biphenyl and the second ammoniums of 20mmol tri- added in 60ml toluene, stirs 20min, and being allowed to be uniformly dispersed add after nitrogen protection is lower
20mmolCuCl, at 20 DEG C 6h is reacted.Room temperature is cooled to after the completion of reaction, crude product is filtered to obtain, crude product is clear with dehydrated alcohol
Wash, the sample for obtaining is vacuum dried into 6h at 80 DEG C, obtain yellow Cu2S presomas.The aforementioned Cu of precise 0.5g2S presomas, so
Afterwards 1h is calcined under 240 DEG C of vacuums, finally give black self assembly Cu2S nanometer sheet.
The Cu that will be prepared2S nanometer sheet carries out transmission electron microscope (TEM) sign, as a result as shown in Figure 5.
Embodiment 3
As shown in Figure 1 technique prepares self assembly Cu2S nanometer plates, by 20mmol 4- hexyloxy -4 '-(10- sulfydryl last of the ten Heavenly stems oxygen
Base) biphenyl and the second ammoniums of 20mmol tri- added in 60ml toluene, stirs 20min, and being allowed to be uniformly dispersed add after nitrogen protection is lower
20mmolCuCl, at 20 DEG C 6h is reacted.Room temperature is cooled to after the completion of reaction, crude product is filtered to obtain, crude product ethanol purge will
The sample for obtaining is vacuum dried 6h at 80 DEG C, obtains yellow Cu2S presomas.The aforementioned Cu of precise 0.5g2S presomas, Ran Hou
1h is calcined under 220 DEG C of argon atmospheres, black self assembly Cu is finally given2S nanometer plates.
The Cu that will be prepared2S nanometer plates carry out transmission electron microscope (TEM) sign, as a result as shown in Figure 6.
Embodiment 4
As shown in Figure 1 technique prepares self assembly Cu2S nano wires, by 20mmol 4- hexyloxy -4 '-(10- sulfydryl fourth oxygen
Base) biphenyl and the second ammoniums of 20mmol tri- added in 60ml toluene, stirs 20min, and being allowed to be uniformly dispersed add after nitrogen protection is lower
20mmolCuCl, at 20 DEG C 6h is reacted.Room temperature is cooled to after the completion of reaction, crude product is filtered to obtain, crude product is clear with dehydrated alcohol
Wash, the sample for obtaining is vacuum dried into 6h at 80 DEG C, obtain yellow Cu2S presoma.The aforementioned Cu2S presomas of precise 0.5g,
Then 1h is calcined under 200 DEG C of vacuums, finally gives black self assembly Cu2S nano wires.
Embodiment 5
As shown in Figure 1 technique prepares self assembly Cu2S nanometer sheet, by 20mmol 4- hexyloxy -4 '-(10- sulfydryl dodecanes
Base) biphenyl and the second ammoniums of 20mmol tri- added in 60ml toluene, stirs 20min, and being allowed to be uniformly dispersed add after nitrogen protection is lower
20mmolCuCl, at 20 DEG C 6h is reacted.Room temperature is cooled to after the completion of reaction, crude product is filtered to obtain, crude product is clear with dehydrated alcohol
Wash, the sample for obtaining is vacuum dried into 6h at 80 DEG C, obtain yellow Cu2S presomas.The aforementioned Cu of precise 0.5g2S presomas, so
Afterwards 1h is calcined under 240 DEG C of vacuums, finally give black self assembly Cu2S nanometer sheet.
Comparative example 1
20mmol 4- hexyloxy -4 '-(10- sulfydryl decyloxies) biphenyl and the second ammoniums of 20mmol tri- are added in 60ml toluene,
Stirring 20min, is allowed to be uniformly dispersed after the lower addition 20mmolCuCl of nitrogen protection, and at 20 DEG C 6h is reacted.It is cold after the completion of reaction
But to room temperature, crude product is filtered to obtain, the sample for obtaining is vacuum dried 6h, obtains yellow by crude product ethanol purge at 80 DEG C
Cu2S presomas.The aforementioned Cu of precise 0.5g2S presomas, then calcine 1h under 240 DEG C of argon atmospheres, obtain size point
The uneven Cu of cloth2S nanometer plates.
The Cu that will be prepared2S nanometer plates carry out transmission electron microscope (TEM) sign, as a result as shown in Figure 7.
Comparative example 2
20mmol lauryl mercaptans and the second ammoniums of 22mmol tri- are added in 60ml toluene, 20min is stirred, dispersion is allowed to equal
It is even to add 20mmolCuCl under nitrogen protection, react 6h at 20 DEG C.Room temperature is cooled to after the completion of reaction, filters slightly to produce
The sample for obtaining is vacuum dried 6h by thing, crude product ethanol purge at 100 DEG C, obtains white Cu2S presomas.Precise
The 0.5g Cu2S presomas, under 200 DEG C of vacuums 1h is calcined, and obtains the uneven Cu of distribution of sizes2S nano-particle.
The Cu that will be prepared2S nano-particle carries out transmission electron microscope (TEM) sign, as a result as shown in Figure 8.
Claims (7)
1. a kind of different-shape self assembly Cu2The preparation method of S nano materials, it is characterised in that comprise the following steps：
(1) by biphenyl mercaptan, acid binding agent and toluene mix homogeneously, Cu-lyt., the biphenyl mercaptan are added under nitrogen protection
It is 1 with the mol ratio of Cu-lyt.:1～1.2:1, react 2～6h in 10～30 DEG C；
(2) reacting liquid filtering for preparing step (1), gained filter cake absolute ethanol washing is subsequently vacuum dried filter cake
To Cu2S presomas；
(3) Cu for preparing step (2)2S presomas are calcined under vacuum or atmosphere of inert gases, when in vacuum
During atmosphere, calcining heat is 200～240 DEG C；When in atmosphere of inert gases, calcining heat is 200～220 DEG C, is obtained not
With pattern self assembly Cu2S nano materials.
2. a kind of different-shape self assembly Cu according to claim 12The preparation method of S nano materials, it is characterised in that
Biphenyl mercaptan described in the step (1) is represented with formula (1)：
3. a kind of different-shape self assembly Cu according to claim 12The preparation method of S nano materials, it is characterised in that
Acid binding agent described in the step (1) is one or more in triethylamine, ammonium acetate and pyridine.
4. a kind of different-shape self assembly Cu according to claim 12The preparation method of S nano materials, it is characterised in that
Using the dehydrated alcohol relative to 1～3 times of volume of reactant liquor during absolute ethanol washing filter cake described in the step (2)
Washed.
5. a kind of different-shape self assembly Cu according to claim 12The preparation method of S nano materials, it is characterised in that
The baking temperature of filter cake described in the step (2) is 80～100 DEG C, and drying time is 4～6h.
6. a kind of different-shape self assembly Cu according to claim 12The preparation method of S nano materials, it is characterised in that
Noble gases described in the step (3) are helium, neon or argon.
7. a kind of different-shape self assembly Cu according to claim 12The preparation method of S nano materials, it is characterised in that
Calcination time is 1～3h in the step (3).
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| CN108383149B (en) * | 2018-05-10 | 2019-10-29 | 南京晓庄学院 | Cu2The nanocrystalline controllable synthesis method of S |
| CN108950585B (en) * | 2018-08-03 | 2020-04-17 | 武汉工程大学 | MoS2@ Cu2S @ foam copper composite nano material and preparation method and application thereof |
| CN114437708B (en) * | 2020-11-05 | 2023-10-24 | 中国科学院化学研究所 | Temperature-sensitive quasi-cuprous sulfide light-emitting two-dimensional semiconductor and preparation method and application thereof |
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