CN101486487A - Zinc sulfide micron hollow sphere and preparation method thereof - Google Patents
Zinc sulfide micron hollow sphere and preparation method thereof Download PDFInfo
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- CN101486487A CN101486487A CNA2008100194887A CN200810019488A CN101486487A CN 101486487 A CN101486487 A CN 101486487A CN A2008100194887 A CNA2008100194887 A CN A2008100194887A CN 200810019488 A CN200810019488 A CN 200810019488A CN 101486487 A CN101486487 A CN 101486487A
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- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 60
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052984 zinc sulfide Inorganic materials 0.000 title abstract description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000001291 vacuum drying Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 76
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 39
- -1 polyoxyethylene Polymers 0.000 claims description 39
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000011010 flushing procedure Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000002073 nanorod Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000002537 cosmetic Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000001069 Raman spectroscopy Methods 0.000 description 13
- 230000003595 spectral effect Effects 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000008118 PEG 6000 Substances 0.000 description 6
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 240000007762 Ficus drupacea Species 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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Abstract
The invention discloses a zinc sulfide micron hollow sphere and a preparation method thereof. The hollow sphere comprises zinc sulfide, particularly the zinc sulfide is a micron hollow sphere, the sphere diameter of the micron hollow sphere is 0.7-6.5 microns, the spherical shell is composed of a nanorod array, the rod axis of the nanorod array points to the sphere center of the micron hollow sphere, the rod length of the nanorod is 100-400 nm, and the rod diameter of the nanorod is 50-200 nm; the method comprises a hydrothermal method and comprises the following steps: in the first step, Miao is addedMixing zinc nitrate, thioacetamide and water to obtain a precursor solution, wherein the weight ratio of the zinc nitrate to the thioacetamide to the water is 0.4-0.6: 0.1-0.3: 20-30; secondly, the precursor solution is firstly placed at the pressure of 5-8 multiplied by 105Pa, reacting at the temperature of 180-220 ℃ for 8-15 h to obtain a precipitate, washing the precipitate with a solvent, and performing vacuum drying treatment to obtain the zinc sulfide micron hollow sphere. The preparation method can be widely applied to the fields of pharmaceutical engineering, cosmetics, biotechnology, photocatalysis, photonic devices and the like, and has the advantages of simple and convenient preparation method, less material consumption and no pollution.
Description
Technical field
The present invention relates to a kind of hollow ball and method for making, especially a kind of Zinc sulphide micron hollow sphere and preparation method thereof.
Background technology
Zinc sulphide (ZnS) is typical direct band gap, short wavelength II-VI family semiconductor material.Its greater band gap, the exciton effect at room temperature just clearly, relatively be fit to make opto-electronic device, as high density information read-write device, full-color display spare, electrooptical device, device for non-linear optical, underwater communication device, biology and engineering in medicine device etc.Simultaneously, ZnS has higher infrared transmission performance and excellent light, thermal properties at infrared band, is good aircraft and laser window material.In addition, nanometer ZnS has gas-sensitive property, and hydrogen sulfide is had higher susceptibility and selectivity, can be used as senser element.ZnS also has excellent photocatalysis performance, can be used for the CO that degrades
2Because its important use is worth, the synthetic of the ZnS of different structure is the focus of research and development always.
At present, synthetic variform ZnS structure is as nano-powder, nanometer rod, nanometer sheet, nano belt etc.Hollow ball structure is because its special structure and surface properties have caused that people note widely, and it has important use in many-sides such as medicine engineering, makeup, biotechnology, photochemical catalysis and photonic devices and is worth.For this reason; people have made unremitting effort; attempt to prepare nanometer or micron-sized zinc sulphide hollow ball, once disclosed a kind of zinc sulphide hollow ball and synthetic method thereof as " SCI " the 26th volume the 2nd interim " ternary additive water solution system synthesizing submicron zinc sulphide hollow ball " literary composition of publishing in February, 2005.It is intended to utilize bionical synthetic method to obtain the zinc sulphide hollow ball.When synthetic, successively polyoxyethylene glycol, methacrylic acid, hydrochloric acid and sodium laurylsulfonate are mixed mutually, and then reacted 24 hours to wherein adding zinc chloride and thioacetyl ammonium, afterwards, with reaction solution cooling, filtration, washing and dry, the acquisition sphere diameter is that 300～400nm, shell thickness are the zinc sulphide hollow ball of 50nm, and the spherical shell of this hollow ball is after the particle of 15nm is formed vermiform or corynebacterium by diameter, merges mutually disorderly and forms.But this hollow ball and synthetic method thereof all exist weak point, and at first, the club that constitutes spherical shell is not the arrangement that is orderly, constitute housing but pile up the back desultorily, and this may produce adverse influence to the controllability of zinc sulfide nano effect; Secondly, synthetic method need be with more raw material, and technology is more numerous and diverse, easy contaminate environment.
Summary of the invention
The technical problem to be solved in the present invention is for overcoming weak point of the prior art, the Zinc sulphide micron hollow sphere that provides a kind of hollow ball shell to be made of nanometer stick array.
Another technical problem that the present invention will solve is for providing a kind of preparation method the preparation method of easy Zinc sulphide micron hollow sphere.
For solving technical problem of the present invention, the technical scheme that is adopted is: Zinc sulphide micron hollow sphere comprises zinc sulphide, particularly said zinc sulphide is the micrometre hollow sphere shape, the sphere diameter of said micrometre hollow sphere is that 0.7～6.5 μ m, spherical shell are made of nanometer stick array, the centre of sphere of the said micrometre hollow sphere of excellent orientation of its axis of said nanometer stick array, the rod length of said nanometer rod are that 100～400nm, rod footpath are 50～200nm.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of Zinc sulphide micron hollow sphere comprises hydrothermal method, and particularly it is finished according to the following steps: the first step, and with zinc nitrate (Zn (NO
3)
2), thioacetamide (TAA) and water mix and obtain precursor solution, wherein, the weight ratio between zinc nitrate, thioacetamide and the water is 0.4～0.6:0.1～0.3:20～30; In second step, earlier precursor solution being placed pressure is 5～8 * 10
5Pa, temperature be 180～220 ℃ down reaction 8～15h obtain precipitated product, again to precipitated product with solvent washing and vacuum drying treatment, make Zinc sulphide micron hollow sphere.
As the preparation method's of Zinc sulphide micron hollow sphere further improvement, described water is deionized water or distilled water; Described before with the precursor solution reaction, to wherein adding polyoxyethylene glycol (PEG), wherein, the weight ratio between polyoxyethylene glycol and the zinc nitrate is 0.2～0.4:0.4～0.6 under stirring; The molecular weight of described polyoxyethylene glycol is 800mol/g or 2000mol/g or 4000mol/g or 6000mol/g or 20000mol/g; The stirring velocity that described polyoxyethylene glycol adds in the precursor solution is that 100～300rpm/min, churning time are 10～30min; After described precursor solution reaction finishes, obtain precipitated product through centrifugal treating, centrifugal speed is 4000～6000rpm/min, centrifugal time 〉=1min; Described flushing solvent is deionized water or distilled water or dehydrated alcohol, and the number of times of flushing is 3～6 times; Vacuum tightness during described vacuum drying treatment is≤1 * 10
-5Pa; Described drying treatment is in 50～70 ℃ of following heating under vacuum 3～4h.
Beneficial effect with respect to prior art is, one, use field emission scanning electron microscope, transmission electron microscope and x-ray diffractometer to carry out the sign of form, structure and composition respectively to the final product that makes, from the stereoscan photograph, transmission electron microscope photo and the X-ray diffraction spectrogram that obtain as can be known, final product is a globe, and the sphere diameter of globe is 0.7～6.5 μ m.The centre of sphere of globe is a hollow form, and promptly globe is a hollow ball, and the spherical shell of hollow ball is made of the nanometer stick array of ordered arrangement, and the excellent axis of nanometer stick array all points to the centre of sphere of hollow ball.The rod length of forming the nanometer rod of excellent array is that 100～400nm, rod footpath are 50～200nm.Nanometer rod is made of single crystal zinc blende; They are two years old, use confocal laser Raman spectroscopy and fluorescence spectrophotometer to test respectively to Zinc sulphide micron hollow sphere, by the result of confocal laser Raman spectroscopy test as can be known, Zinc sulphide micron hollow sphere has tangible six grades of vertical optical phonon Raman scattering moulds, and weak multi-stage surface optical phonon Raman scattering mould.By the result of fluorescence spectrophotometer test as can be known, the Zinc sulphide micron hollow sphere of different size exists two glow peaks, a blue region at 3.0eV, and another is in the green glow zone of 2.4eV.Above-mentioned test result shows that the excellent properties of Zinc sulphide micron hollow sphere all has the potential application prospect in fields such as biomarker, photoelectric devices; Its three, method is simple and convenient, materials are few, and are pollution-free, belong to green synthesis techniques, production efficiency height, the utmost point are suitable for industrialized scale operation.
Further embodiment as beneficial effect, the one, before with the precursor solution reaction, in stirring down to wherein adding polyoxyethylene glycol, wherein, weight ratio between polyoxyethylene glycol and the zinc nitrate is preferably 0.2～0.4:0.4～0.6, make precursor solution under the structure-directing effect of polyoxyethylene glycol, the structure of the final product Zinc sulphide micron hollow sphere of generation was both stable, and its sphere diameter can be controlled again in the larger context artificially; The 2nd, the molecular weight of polyoxyethylene glycol is preferably 800mol/g or 2000mol/g or 4000mol/g or 6000mol/g or 20000mol/g, can make by selection the polyoxyethylene glycol chain length, change the size of sphere aggregates, thereby realize accurate control the Zinc sulphide micron hollow sphere sphere diameter; The 3rd, the stirring velocity in the polyoxyethylene glycol adding precursor solution is preferably 100～300rpm/min, churning time is preferably 10～30min, and polyoxyethylene glycol and precursor solution are mixed fully; The 4th, precursor solution reaction obtains precipitated product through centrifugal treating after finishing, and centrifugal speed is preferably 4000～6000rpm/min, centrifugal time preferred 〉=1min is easy to obtain quickly final product; The 5th, flushing is preferably deionized water or distilled water or dehydrated alcohol with solvent, and the number of times of flushing is preferably 3～6 times, has not only avoided the introducing of impurity, also only needs less wash number just can reach the purpose of cleaning; The 6th, the vacuum tightness during vacuum drying treatment is preferably≤and 1 * 10
-5Pa, drying treatment is preferably in 50～70 ℃ of following heating under vacuum 3～4h, except that having guaranteed that zinc sulphide is not oxidized, goes back the energy-and time-economizing.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 is after the hollow ball that will make is distributed on the slide glass equably, re-uses the XRD figure spectrum that obtains after PhilipsX ' Pert type X-ray diffraction (XRD) instrument is tested it, and the ordinate zou among the figure is a relative intensity, and X-coordinate is a diffraction angle.Curve (1), curve (2) and curve (3) in the XRD figure spectrum be respectively use molecular weight as the polyoxyethylene glycol (PEG-4000) of 4000mol/g, molecular weight as the polyoxyethylene glycol (PEG-800) of 800mol/g with the spectral line of the hollow ball when not using polyoxyethylene glycol.This XRD figure spectrum demonstrates, all diffraction peaks of the prepared hollow ball of different PEG chain lengths can both index be a cube phase, diffraction peak with ZnS of zincblende lattce structure, and can be well and the Data Matching of JCPDS card (No.80-0020) report, the diffractive features peak of other impurity do not found;
Fig. 2 is use PEG-4000 when the preparation hollow ball after, take the photograph after using U.S. FEI Sirion 200 type field emission scanning electron microscopes (SEM) to observe to the hollow ball that repeatedly makes many high resolving power SEM photos in one of, can see by this photo, the final product overwhelming majority is the spheroidal particle of rule, and output is very big.Can see that from the interior illustration in the photo upper right corner diameter of zinc sulphide bead is about 4.5 μ m, the surface ratio of spherical shell is more coarse.Ball is the micron ball of hollow, and the shell of ball is made up of the nanometer rod of about 240nm;
Fig. 3 is use PEG-4000, PEG-6000 respectively when the preparation hollow ball after, to the hollow ball that repeatedly makes use JEOL-2010 type high resolution transmission electron microscope (TEM) observe in many TEM photos of taking the back one of, wherein, Fig. 3 a is the TEM image of the single hollow ball cut place correspondence shown in the interior illustration in Fig. 2 upper right corner.Fig. 3 b is the high resolving power TEM image of the further amplification of the place of hollow ball cut shown in Fig. 3 a correspondence.Fig. 3 c is the selected area electron diffraction style (SAED) of the place of hollow ball cut shown in Fig. 3 b correspondence.Half broken pairing TEM image of hollow ball of zinc sulphide that Fig. 3 d makes for using PEG-6000.By finding out among Fig. 3 a, Fig. 3 d that hollow ball is made up of nanometer rod, nanometer rod is arranged and has been self-assembled into hollow ball.The diameter of the zinc sulfide nano rod that obtains is smaller, is easily seen through by electronic number.By Fig. 3 c as can be known, nanometer rod is a monocrystalline, although there is other diffraction spot to occur, that is just because the diameter of electron beam is bigger.Hollow ball is that the nanometer rod by monocrystalline constitutes;
Fig. 4 does not use PEG respectively when the preparation hollow ball, after having used PEG-800, PEG-2000, PEG-4000, PEG-6000 and PEG-20000, take the photograph after using U.S. FEISirion 200 type field emission scanning electron microscopes (SEM) to observe to the hollow ball that repeatedly makes many SEM photos in one of.Wherein, Fig. 4 a can find out by it for the SEM photo of the hollow ball that do not use PEG and make, do not use the diameter of the hollow ball that PEG makes even, is about 0.7 μ m, and its shell wall is made up of the nanometer rod of tens nanometers.Fig. 4 b can be found out by it that for the SEM photo of the hollow ball that uses PEG-800 and make the sphere diameter of the hollow ball that makes is about 2 μ m.Fig. 4 c can be found out by it that for the SEM photo of the hollow ball that uses PEG-2000 and make the sphere diameter of the hollow ball that makes is about 4 μ m.Fig. 4 d is the SEM photo of the hollow ball that uses PEG-4000 and make, and the interior illustration in this photo upper right corner breaks the SEM photo of ball for its part, can be found out that by it sphere diameter of the hollow ball that makes is about 4.5 μ m.Fig. 4 e is the SEM photo of the hollow ball that uses PEG-6000 and make, the interior illustration in this photo upper left corner is the SEM photo of the broken ball of its part, can find out by it, the sphere diameter of the hollow ball that makes is about 5 μ m, can find out that by interior illustration ball is a hollow form, spherical shell be by diameter be about 105nm, the nanometer rod self-assembly that is about to 250nm forms.Fig. 4 f can be found out by it that for the SEM photo of the hollow ball that uses PEG-20000 and make the sphere diameter of the hollow ball that makes is about 6.5 μ m, ball hollow, spherical shell be by diameter be about 200nm, the nanometer rod self-assembly that is about to 400nm forms.
Fig. 5 has used PEG-6000, PEG-4000, PEG-2000 and PEG-800 respectively when the preparation hollow ball, and after not using PEG, be scattered in the hollow ball that makes on the silicon substrate respectively, re-use that LABRAM-HR type confocal laser Raman spectroscopy is tested and the spectrum that obtains, used excitation light source is that wavelength is the He-Cd laser apparatus of 325nm during test.Curve in the spectrum (5) is the resonance raman spectral line of the hollow ball that use PEG-800 make, curve (1) resonance raman spectral line for the hollow ball that do not use PEG make for the resonance raman spectral line of the hollow ball that uses PEG-4000 and make, curve (3) for the resonance raman spectral line of the hollow ball that uses PEG-2000 and make, curve (2) for the resonance raman spectral line of the hollow ball that uses PEG-6000 and make, curve (4).As seen from Figure 5, use the prepared hollow ball of PEG with different chain length that six sharp-pointed peaks of significantly vertical optical phonon (LO) are all arranged, their center lays respectively at 348.1cm
-1, 696.5cm
-1, 1045.1cm
-1, 1393.2cm
-1, 1740.3cm
-1And 2090cm-
1, be single order LO phonon mid-frequency (348.1cm
-1) multiple.When excitation energy during near three rank, quadravalence phon scattering energy, it is strong that three rank, quadravalence phon scattering and exciting light resonance cause three rank, quadravalence phon scattering peak is better than other phon scattering peak.Except six sharp-pointed peaks of vertical optical phonon (LO), also observe weak multi-stage surface optical phonon Raman scattering peak (SO), its single order SO phonon mid-frequency approximately is positioned at 332cm
-1The place is between longitudinal optical phonon and lateral optical phonon frequency.And, along with reducing of PEG chain length, the peak at Raman peaks LO and SO peak by force with and the fluorescence peak back of the body reduce at the end, this may be that dimensional effect by the nanometer rod of zinc sulphide causes;
Fig. 6 has used PEG-4000 and PEG-800 respectively when the preparation hollow ball, and after not using PEG, be scattered in the hollow ball that makes on the silicon substrate respectively, re-use that LABRAM-HR type confocal laser Raman spectroscopy and its fluorescence spectrophotometer that carries are tested and the spectrum that obtains, used excitation light source is that wavelength is the He-Cd laser apparatus of 325nm during test.Curve in the spectrum (1) is the photoluminescence spectral line of the hollow ball that uses PEG-4000 and make, curve (3) the photoluminescence spectral line for the hollow ball that do not use PEG and make for the photoluminescence spectral line of the hollow ball that uses PEG-800 and make, curve (2).As seen from Figure 6, use the prepared hollow ball of PEG that the blue light at 3.0eV place and two glow peaks of green glow at 2.4eV place are arranged with different chain length.Because raw materials used purity is very high, so think that these two emission spectrums launch owing to defective.May cause with sulphur room luminous in the blue emission at 3.0eV place spectrum, and compose and to cause with zinc room luminous in the green emitted at 2.4eV place.
Embodiment
At first make or buy zinc nitrate (Zn (NO from market with ordinary method
3)
2), thioacetamide (TAA), deionized water, distilled water, dehydrated alcohol and polyoxyethylene glycol (PEG), wherein, the molecular weight of polyoxyethylene glycol is 800mol/g, 2000mol/g, 4000mol/g, 6000mol/g and 20000mol/g.Then,
Embodiment 1: finish preparation according to the following steps successively: the first step, zinc nitrate, thioacetamide and water mixing are obtained precursor solution, and the weight ratio between the zinc nitrate in the precursor solution, thioacetamide and the water is 0.4:0.3:20; Wherein, water is deionized water.In second step, earlier precursor solution being placed pressure is 5 * 10
5Pa, temperature be 180 ℃ down reaction 15h obtain precipitated product, again to precipitated product with solvent washing and vacuum drying treatment; Wherein, after the precursor solution reaction finishes, obtain precipitated product through centrifugal treating, centrifugal speed is that 4000rpm/min, centrifugal time are 5min, and flushing is a deionized water with solvent, and the number of times of flushing is 3 times, and the vacuum tightness during vacuum drying treatment is 1 * 10
-5Pa, drying treatment is in 50 ℃ of following heating under vacuum 4h.Make a as Fig. 4, and as curve (1) among the curve among Fig. 1 (3), Fig. 5 and the Zinc sulphide micron hollow sphere shown in the curve (3) among Fig. 6.
Embodiment 2: finish preparation according to the following steps successively: the first step, zinc nitrate, thioacetamide and water mixing are obtained precursor solution, and the weight ratio between the zinc nitrate in the precursor solution, thioacetamide and the water is 0.45:0.25:23; Wherein, water is distilled water.Afterwards, add polyoxyethylene glycol in the precursor solution under stirring, wherein, the weight ratio between polyoxyethylene glycol and the zinc nitrate is 0.2:0.45, the molecular weight of polyoxyethylene glycol is 4000mol/g, and the stirring velocity that polyoxyethylene glycol adds in the precursor solution is that 100rpm/min, churning time are 30min.In second step, earlier precursor solution being placed pressure is 6 * 10
5Pa, temperature be 190 ℃ down reaction 13h obtain precipitated product, again to precipitated product with solvent washing and vacuum drying treatment; Wherein, after the precursor solution reaction finishes, obtain precipitated product through centrifugal treating, centrifugal speed is that 4500rpm/min, centrifugal time are 4min, and flushing is a distilled water with solvent, and the number of times of flushing is 4 times, and the vacuum tightness during vacuum drying treatment is 1 * 10
-5Pa, drying treatment is in 55 ℃ of following heating under vacuum 4h.Make and be similar to Fig. 2, Fig. 3 a, Fig. 3 b, Fig. 3 c and Fig. 4 d, and as curve (4) among the curve among Fig. 1 (1), Fig. 5 and the Zinc sulphide micron hollow sphere shown in the curve (2) among Fig. 6.
Embodiment 3: finish preparation according to the following steps successively: the first step, zinc nitrate, thioacetamide and water mixing are obtained precursor solution, and the weight ratio between the zinc nitrate in the precursor solution, thioacetamide and the water is 0.5:0.2:25; Wherein, water is deionized water.Afterwards, add polyoxyethylene glycol in the precursor solution under stirring, wherein, the weight ratio between polyoxyethylene glycol and the zinc nitrate is 0.3:0.5, the molecular weight of polyoxyethylene glycol is 4000mol/g, and the stirring velocity that polyoxyethylene glycol adds in the precursor solution is that 200rpm/min, churning time are 25min.In second step, earlier precursor solution being placed pressure is 7 * 10
5Pa, temperature be 200 ℃ down reaction 12h obtain precipitated product, again to precipitated product with solvent washing and vacuum drying treatment; Wherein, after the precursor solution reaction finishes, obtain precipitated product through centrifugal treating, centrifugal speed is that 5000rpm/min, centrifugal time are 3min, and flushing is a dehydrated alcohol with solvent, and the number of times of flushing is 5 times, and the vacuum tightness during vacuum drying treatment is 1 * 10
-5Pa, drying treatment is in 60 ℃ of following heating under vacuum 3.5h.Make as Fig. 2, Fig. 3 a, Fig. 3 b, Fig. 3 c and Fig. 4 d, and as curve (4) among the curve among Fig. 1 (1), Fig. 5 and the Zinc sulphide micron hollow sphere shown in the curve (2) among Fig. 6.
Embodiment 4: finish preparation according to the following steps successively: the first step, zinc nitrate, thioacetamide and water mixing are obtained precursor solution, and the weight ratio between the zinc nitrate in the precursor solution, thioacetamide and the water is 0.55:0.15:28; Wherein, water is distilled water.Afterwards, add polyoxyethylene glycol in the precursor solution under stirring, wherein, the weight ratio between polyoxyethylene glycol and the zinc nitrate is 0.35:0.55, the molecular weight of polyoxyethylene glycol is 4000mol/g, and the stirring velocity that polyoxyethylene glycol adds in the precursor solution is that 200rpm/min, churning time are 20min.In second step, earlier precursor solution being placed pressure is 7 * 10
5Pa, temperature be 210 ℃ down reaction 10h obtain precipitated product, again to precipitated product with solvent washing and vacuum drying treatment; Wherein, after the precursor solution reaction finishes, obtain precipitated product through centrifugal treating, centrifugal speed is that 5500rpm/min, centrifugal time are 2min, and flushing is a deionized water with solvent, and the number of times of flushing is 5 times, and the vacuum tightness during vacuum drying treatment is 1 * 10
-5Pa, drying treatment is in 65 ℃ of following heating under vacuum 3h.Make and be similar to Fig. 2, Fig. 3 a, Fig. 3 b, Fig. 3 c and Fig. 4 d, and as curve (4) among the curve among Fig. 1 (1), Fig. 5 and the Zinc sulphide micron hollow sphere shown in the curve (2) among Fig. 6.
Embodiment 5: finish preparation according to the following steps successively: the first step, zinc nitrate, thioacetamide and water mixing are obtained precursor solution, and the weight ratio between the zinc nitrate in the precursor solution, thioacetamide and the water is 0.6:0.1:30; Wherein, water is deionized water.Afterwards, add polyoxyethylene glycol in the precursor solution under stirring, wherein, the weight ratio between polyoxyethylene glycol and the zinc nitrate is 0.4:0.6, the molecular weight of polyoxyethylene glycol is 4000mol/g, and the stirring velocity that polyoxyethylene glycol adds in the precursor solution is that 300rpm/min, churning time are 10min.In second step, earlier precursor solution being placed pressure is 8 * 10
5Pa, temperature be 220 ℃ down reaction 8h obtain precipitated product, again to precipitated product with solvent washing and vacuum drying treatment; Wherein, after the precursor solution reaction finishes, obtain precipitated product through centrifugal treating, centrifugal speed is that 6000rpm/min, centrifugal time are 1min, and flushing is a distilled water with solvent, and the number of times of flushing is 6 times, and the vacuum tightness during vacuum drying treatment is 1 * 10
-5Pa, drying treatment is in 70 ℃ of following heating under vacuum 3h.Make and be similar to Fig. 2, Fig. 3 a, Fig. 3 b, Fig. 3 c and Fig. 4 d, and as curve (4) among the curve among Fig. 1 (1), Fig. 5 and the Zinc sulphide micron hollow sphere shown in the curve (2) among Fig. 6.
Again respectively without polyoxyethylene glycol or to select the molecular weight of polyoxyethylene glycol for use be 800mol/g or 2000mol/g or 6000mol/g or 20000mol/g, repeat the foregoing description 1～5, make equally as or be similar to Fig. 2～4 and as or be similar to the Zinc sulphide micron hollow sphere shown in the curve among Fig. 1, Fig. 5 and Fig. 6.
Obviously, those skilled in the art can carry out various changes and modification to Zinc sulphide micron hollow sphere of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1, a kind of Zinc sulphide micron hollow sphere, comprise zinc sulphide, it is characterized in that said zinc sulphide is the micrometre hollow sphere shape, the sphere diameter of said micrometre hollow sphere is that 0.7～6.5 μ m, spherical shell are made of nanometer stick array, the centre of sphere of the said micrometre hollow sphere of excellent orientation of its axis of said nanometer stick array, the rod length of said nanometer rod are that 100～400nm, rod footpath are 50～200nm.
2, the preparation method of Zinc sulphide micron hollow sphere according to claim 1 comprises hydrothermal method, it is characterized in that finishing according to the following steps:
The first step obtains precursor solution with zinc nitrate, thioacetamide and water mixing, and wherein, the weight ratio between zinc nitrate, thioacetamide and the water is 0.4～0.6: 0.1～0.3: 20～30;
In second step, earlier precursor solution being placed pressure is 5～8 * 10
5Pa, temperature be 180～220 ℃ down reaction 8～15h obtain precipitated product, again to precipitated product with solvent washing and vacuum drying treatment, make Zinc sulphide micron hollow sphere.
3, the preparation method of Zinc sulphide micron hollow sphere according to claim 2 is characterized in that water is deionized water or distilled water.
4, the preparation method of Zinc sulphide micron hollow sphere according to claim 2, it is characterized in that before the precursor solution reaction, to wherein adding polyoxyethylene glycol, wherein, the weight ratio between polyoxyethylene glycol and the zinc nitrate is 0.2～0.4:0.4～0.6 under stirring.
5, the preparation method of Zinc sulphide micron hollow sphere according to claim 4, the molecular weight that it is characterized in that polyoxyethylene glycol is 800mol/g or 2000mol/g or 4000mol/g or 6000mol/g or 20000mol/g.
6, the preparation method of Zinc sulphide micron hollow sphere according to claim 5 is characterized in that the stirring velocity that polyoxyethylene glycol adds in the precursor solution is that 100～300rpm/min, churning time are 10～30min.
7, the preparation method of Zinc sulphide micron hollow sphere according to claim 2, it is characterized in that precursor solution reaction finishes after, obtain precipitated product through centrifugal treating, centrifugal speed is 4000～6000rpm/min, centrifugal time 〉=1min.
8, the preparation method of Zinc sulphide micron hollow sphere according to claim 2 is characterized in that flushing is deionized water or distilled water or dehydrated alcohol with solvent, and the number of times of flushing is 3～6 times.
9, the preparation method of Zinc sulphide micron hollow sphere according to claim 2, the vacuum tightness when it is characterized in that vacuum drying treatment is≤1 * 10
-5Pa.
10, the preparation method of Zinc sulphide micron hollow sphere according to claim 9 is characterized in that drying treatment is in 50～70 ℃ of following heating under vacuum 3～4h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803636A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc sulfide nuclear hollow microspheres |
| CN106517308A (en) * | 2015-09-15 | 2017-03-22 | 宿迁学院 | Preparation method of ZnS hollow microspheres |
| CN106745197A (en) * | 2016-11-17 | 2017-05-31 | 新疆维吾尔自治区产品质量监督检验研究院 | ZnS micron balls and preparation method thereof |
| CN106927498A (en) * | 2017-03-14 | 2017-07-07 | 中南大学 | A kind of zinc sulfide nano-belt, preparation and its application in lithium sulfur battery anode material is prepared |
| CN114455626A (en) * | 2022-02-25 | 2022-05-10 | 广东鑫达新材料科技有限公司 | Beta-type active zinc sulfide and preparation method thereof |
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2008
- 2008-01-16 CN CNA2008100194887A patent/CN101486487A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803636A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc sulfide nuclear hollow microspheres |
| CN103803636B (en) * | 2012-11-14 | 2015-04-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc sulfide nuclear hollow microspheres |
| CN106517308A (en) * | 2015-09-15 | 2017-03-22 | 宿迁学院 | Preparation method of ZnS hollow microspheres |
| CN106745197A (en) * | 2016-11-17 | 2017-05-31 | 新疆维吾尔自治区产品质量监督检验研究院 | ZnS micron balls and preparation method thereof |
| CN106927498A (en) * | 2017-03-14 | 2017-07-07 | 中南大学 | A kind of zinc sulfide nano-belt, preparation and its application in lithium sulfur battery anode material is prepared |
| CN106927498B (en) * | 2017-03-14 | 2019-08-16 | 中南大学 | A kind of zinc sulfide nano-belt, preparation and its preparing the application in lithium sulfur battery anode material |
| CN114455626A (en) * | 2022-02-25 | 2022-05-10 | 广东鑫达新材料科技有限公司 | Beta-type active zinc sulfide and preparation method thereof |
| WO2023160008A1 (en) * | 2022-02-25 | 2023-08-31 | 广东鑫达新材料科技有限公司 | β-TYPE ACTIVATED ZINC SULFIDE AND PREPARATION METHOD THEREFOR |
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