CN101759226B - Binary sulfide CuXZn1-XS particle with efflorescent structure and preparation method thereof - Google Patents
Binary sulfide CuXZn1-XS particle with efflorescent structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a binary sulfide CuXZn1-XS particle with an efflorescent structure and a preparation method thereof, belonging to the technical field of semiconductor material; the binary sulfide is formed by two metal centers, the molecular formula is CuXZn1-XS, X is 0.85-0.95, and the appearance of the particle is efflorescent; the preparation method comprises the following steps: unitary zinc sulfide particles with the efflorescent structure are prepared by adopting a low-temperature solvent hot method, and then the prepared efflorescent zinc sulfide powder is placed in the solution containing Cu2+, after short-time room-temperature treatment, the binary sulfide CuXZn1-XS with the same shape with the-precursor zinc sulfide is obtained; compared with the sulfide, the binary sulfide has abundant metal centers, thereby having abundant band gaps; in addition, the central metals of compound can be controllably regulated by adopting a simple replacement method, thereby having important significance to crystal engineering research.
Description
Technical field
The invention belongs to technical field of semiconductor, be specifically related to a kind of binary sulfide Cu with flower-like structure
XZn
1-XS particulate and preparation method thereof.
Background technology
Semiconductor nano material has the potential using value at aspects such as optics, electricity, magnetics, nanoelectronicss, is one of research focus of modern chemistry, material and physical science.Metallic sulfide is a kind of very important semiconductor material.For example, zinc sulphide (ZnS) is a kind of II-IV family direct band-gap semicondictor, and energy gap is 3.6～3.8eV, is widely used in fields such as semi-conductor, pigment, pl-, solar cell, infrared eye, gas sensor.
Nano-zinc sulfide can not only cause absorbing wavelength and fluorescence blue shift, can also produce non-linear optical effect, and strengthens the redox ability of nanoparticle, has more excellent photoelectric catalytic activity.Therefore, also just most important based on the study on the modification of nano-zinc sulfide material.The method of modifying that generally adopts is through electroless plating method or solution-deposition method material to be carried out the surface to coat.But common employed electroless plating method is harsh to conditional request, and brings pollution easily, though and solution-deposition method is simpler relatively, coating layer and product combine but that undertighten is firm, cause coating layer to come off easily.Therefore, can improve the simple of nano-zinc sulfide performance and effectively novel method be very worth expectation.
The energy gap of cupric sulfide then can change with the variation of its valence state, like Cu
2S, Cu
18The energy gap of S and CuS is respectively 1.2,1.5 and 2.0eV.Synthetic binary complex copper zinc sulfide then can further improve the semiconducting behavior of transient metal sulfide, because polynary sulfide can be introduced changeable energy level to a certain extent.But the settling velocity in the reaction process of different metal ion and sulphur source (sulphur powder, thiocarbamide, thioacetamide, sodium sulphite etc.) is asynchronous, so that compound inhomogeneous, the pattern of the metal component that common employed codeposition adulterating method will cause product is difficult to control, circulation ratio is relatively poor etc.So, if big, the severe reaction conditions of the synthetic difficulty of the binary sulfide of wanting to adopt the codeposition adulterating method to obtain to form and all effectively controlling, also need in addition can realize under the booster action of outer adding assistants (tensio-active agent, dispersion agent etc.) with pattern.Therefore, how to obtain binary sulfide through simple method and be still the difficult point in the present research work, the method that develops a kind of more effective adjustment sulfide metal center composition and its pattern of ability better controlled so is necessary.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency that exists in the prior art, a kind of binary sulfide Cu with flower-like structure is provided
XZn
1-XS particulate and preparation method thereof, this kind method is simply effective, and the The Nomenclature Composition and Structure of Complexes of resulting material all can effectively be controlled.
For realizing the foregoing invention purpose, the technical scheme that the present invention adopts is following:
Binary sulfide Cu with flower-like structure of the present invention
XZn
1-XThe S particulate, its particle appearance is flower-shaped, consists of the sulfide that two kinds of metal centers constitute, and its molecular formula is Cu
XZn
1-XS, the span of X is 0.85～0.95 in the formula.Described binary sulfide Cu
XZn
1-XThe molar ratio of Cu and Zn is 5～20: 1 among the S.
Described binary sulfide Cu
XZn
1-XThe molar ratio of Cu and Zn can be adjusted in 0.80～0.99 scope in the S particulate.
Described binary sulfide Cu
XZn
1-XThe particle size range of S particulate is 100nm～20 μ m.
This binary sulfide Cu provided by the invention
XZn
1-XThe preparation method of S particulate adopts the preparation of low-temperature solvent heat method to provide the monobasic zinc sulphide particulate of flower-like structure earlier; Place the flower-shaped zinc sulfide powder that makes then and contain in the middle of the copper ion solution, after the short period of time room temperature treatment, can obtain having the binary sulfide Cu of similar pattern with precursor zinc sulphide
XZn
1-XS specifically comprises the steps:
The ZnS powder that (1) will have a flower-like structure joins in the middle of the aqueous solution of soluble copper salt that concentration is 0.01～5mol/L, at room temperature uses high-power magnetic stirring apparatus vigorous stirring after 5～180 minutes, and spinning obtains throw out;
(2) with the throw out that obtains with dilute acid soln washing 2～5 times, water washing 2～5 times in 50～80 ℃ of dryings 5～24 hours, promptly obtains having the binary sulfide Cu of flower-like structure
XZn
1-XThe S particulate.
Described soluble copper salt is selected from the mixing of any one or two or more material in copper sulfate, cupric nitrate, cupric chloride or the neutralized verdigris.
Used dilute acid soln is meant that concentration is a kind of in hydrochloric acid, sulfuric acid, nitric acid or the acetum solution of 0.1～5mol/L.
Compare with sulfide, binary sulfide has abundanter metal center, therefore has abundanter band gap.In addition, forming controlled adjustment through simple method of replacing realization compound core metal, for crystal engineering research, also is very significant.
The present invention utilizes the treated cation method to convert the monobasic sulfide (ZnS) with certain initial configuration into to have the central metal adjustable ratio but the constant binary sulfide (Cu of configuration
XZn
1-XS).Cationic exchange method among the present invention be a kind of in particulate the method for exchange each other between the positively charged ion of original position; This method can be under the prerequisite of the original configuration that keeps initial thing the composition of the central metal element of controlled adjusting material, and then influence the various performances of material.
One of advantage of the present invention is to adopt simple method to prepare a series of binary sulfide Cu with different micron flower-like structures of forming
XZn
1-XThe S particulate.Two of advantage of the present invention is that the base exchange method that is adopted has the appearance structure characteristics that can inherit its initial thing, and this is to obtaining having specific morphology but form different binary sulfide Cu
XZn
1-XThe S particulate is very important.
Description of drawings
Fig. 1 different binary metal sulfide (Cu of composition that to be prepared zinc sulphide (ZnS) obtain with cationic exchange
XZn
1-XS) X-ray diffraction (XRD) collection of illustrative plates.Wherein, a is ESEM (SEM) figure of zinc sulphide, resulting each binary metal sulfide among b, c, d, e, the corresponding embodiment 1,2,3,4,5 of f difference.
Fig. 2 different binary metal sulfide (Cu of composition that to be prepared zinc sulphide (ZnS) obtain with cationic exchange
XZn
1-XS) SEM (sem) figure.Wherein, a is ESEM (SEM) figure of zinc sulphide, resulting each binary metal sulfide among b, c, d, e, the corresponding embodiment 1,2,3,4,5 of f difference.
Fig. 3 be the different binary metal sulfide of the composition that obtains of cationic exchange can spectrogram.Wherein, resulting each binary metal sulfide among a, b, c, d, the corresponding embodiment 1,2,3,4,5 of e difference.
Embodiment
The flower-shaped binary sulfide Cu of micron provided by the invention
XZn
1-XThe S particle is a kind of sulfide with two kinds of metallic element centers, and the ratio of these two kinds of metallic elements can be regulated through the ratio of control reactant.The flower-shaped binary sulfide Cu of micron described in the present invention
XZn
1-XThe S particle has bigger specific surface.
Embodiment 1: flower-shaped binary sulfide Cu
0.85Zn
0.15The preparation of S particulate.
Flower-shaped micrometer structure ZnS's is synthetic:
Accurately take by weighing 0.4561 gram forerunner title complex Zn (phen)
2(H2O)
2]
2L6H
2O (the adjacent phenanthroline of phen=; The synthesizing L=p-methyl benzenesulfonic acid)) in 50 milliliters triangular flask, add 11 milliliters of terepthaloyl moietie, be stirred to the title complex presoma and dissolve fully.Then accurately take by weighing 0.0381 gram thiocarbamide again, be dissolved in 5 milliliters of anhydrous ethylenediamines.The ethylenediamine solution that will be dissolved with thiocarbamide then slowly is added drop-wise in forerunner's complex solution and goes, wait all thiourea solutions all to be added drop-wise to triangular flask after, continue to stir half hour again.At last above-mentioned solution being transferred to 23ml has in the stainless steel still of polytetrafluoroethylliner liner, and the stainless steel still is put into the constant temperature air dry oven.Heating is 24 hours under 125 degree.Take out the stainless steel still, open inner bag, pour out supernatant liquid, with deionized water and absolute ethanol washing deposition several, put into then vacuum drying oven 60 spend under freeze-day with constant temperature 4 hours, products therefrom is flower-shaped micrometer structure ZnS, yield is 83%.
Choose the above-mentioned ZnS material that obtains having flower-like structure as precursor; Place the ZnS powder of 0.2924g among the copper nitrate solution of 75mL 0.01mol/L, reaction is 5 minutes under room temperature, spinning afterwards; Use concentration to be the sulphuric acid soln of 0.1mol/L washing 2 times; Deionized water wash 5 times, resulting solids promptly obtains consisting of Cu in 80 ℃ of dryings 5 hours
0.85Zn
0.15The flower-shaped binary sulfide of S.
The X-ray diffracting spectrum of precursor ZnS is shown in Fig. 1 a, wherein in 2 θ=27.5,29,31,40.5,47.5,52.5, the diffraction peak at 56.5 places can be diffracted to α-ZnS (JCPDS 1-677).Its stereoscan photograph is shown in Fig. 2 a, can be known by large-area particle among the figure, and ZnS is that the spheroidal particle of 0.5～2.5 μ m is formed by particle size range approximately.Illustration among Fig. 2 a is the photo of the bigger multiplying power of its individual particle, and the particle with spherical outward appearance that can see ZnS clearly by figure comes down to have flower-shaped microtexture, and the ZnS precursor that we selected for use thus is to have the flower-like structure particulate.
Form by the energy spectrometer mensuration of being joined in the ESEM through the product after the processing of Cu salts solution.It can see Fig. 3 a by spectrogram, and wherein the characteristic peak of existing Zn also have the characteristic peak of Cu to occur, and the characteristic peak of Cu is very strong, shows that the cupric ion in the solution with the zinc element in the solid ZnS particle permutoid reaction has taken place really.Quantitative power spectrum calculation result shows, Cu in this sample: Zn (mol ratio)=5.7: 1, and then the molecular formula of sample can be write Cu
0.85Zn
0.15S.Cu
0.85Zn
0.15The X-ray diffracting spectrum of S sample is shown in Fig. 1 b; Wherein in 2 θ=27,28.5,30.5,39.5,48,52, the diffraction peak at 56.5 places can be diffracted to the structure of α-ZnS (JCPDS1-677); But there is skew the position of its diffraction peak slightly with initial thing ZnS, and the intensity of diffraction peak is also different.SEM figure shown in Fig. 2 b shows Cu
0.83Zn
0.13The S sample has and similar flower-like structure of ZnS and particle diameter branch.
Embodiment 2: flower-shaped binary sulfide Cu
0.88Zn
0.12The preparation of S particulate.
The ZnS that is selected for use among the ZnS that present embodiment is selected for use and the embodiment 1 is identical.
Choose have flower-like structure the ZnS material as precursor; Place the ZnS powder of 0.2924g among the copper-bath of 30mL 0.05mol/L, reaction is 10 minutes under room temperature, spinning afterwards; Use concentration to be the acetum of 1mol/L washing 3 times; Deionized water wash 4 times, resulting solids promptly obtains consisting of Cu in 70 ℃ of dryings 10 hours
0.88Zn
0.12The flower-shaped binary sulfide of S.
Product after handling through the Cu salts solution can spectrogram shown in Fig. 3 b; The characteristic peak of existing Zn wherein; Also have the characteristic peak of Cu to occur, and the characteristic peak of Cu is very strong, shows that homo-ion in the solution with the zinc element in the solid ZnS particle permutoid reaction taken place really.Quantitative power spectrum calculation result shows, Cu in this sample: Zn (mol ratio)=7.3: 1, and then the molecular formula of sample can be write Cu
0.88Zn
0.12S.Cu
0.88Zn
0.12The X-ray diffracting spectrum of S sample is shown in Fig. 1 c; Wherein in 2 θ=27,28.5,31.5,39.5,48,52, the diffraction peak at 57 places can be diffracted to the structure of α-ZnS (JCPDS 1-677); But there is skew the position of its diffraction peak slightly with initial thing ZnS, and the intensity of diffraction peak is also different.SEM figure shown in Fig. 2 c shows Cu
0.88Zn
0.12The S sample has and similar flower-like structure of ZnS and particle diameter branch.
Embodiment 3: flower-shaped binary sulfide Cu
0.91Zn
0.09The preparation of S particulate.
The ZnS that is selected for use among the ZnS that present embodiment is selected for use and the embodiment 1 is identical.
Choose have flower-like structure the ZnS material as precursor; Place the ZnS powder of 2.924g among the Cupric Chloride Solution of 22.5mL 1mol/L, reaction is 80 minutes under room temperature, uses concentration to wash 4 times as the hydrochloric acid soln of 2mol/L; Deionized water wash 3 times; Spinning afterwards, resulting solids promptly obtains consisting of Cu in 60 ℃ of dryings 15 hours
0.91Zn
0.09The flower-shaped binary sulfide of S.
Product after handling through the Cu salts solution can spectrogram shown in Fig. 3 c; The characteristic peak of existing Zn wherein; Also have the characteristic peak of Cu to occur, and the characteristic peak of Cu is very strong, shows that homo-ion in the solution with the zinc element in the solid ZnS particle permutoid reaction taken place really.Quantitative power spectrum calculation result shows, Cu in this sample: Zn (mol ratio)=10.1: 1, and then the molecular formula of sample can be write Cu
0.91Zn
0.09S.Cu
0.91Zn
0.09The X-ray diffracting spectrum of S sample is shown in Fig. 1 d; Wherein in 2 θ=27.5,29.5,32,39.5,48,53, the diffraction peak at 59 places can be diffracted to the structure of α-ZnS (JCPDS 1-677); But there is skew the position of its diffraction peak slightly with initial thing ZnS, and the intensity of diffraction peak is also different.SEM figure shown in Fig. 2 d shows Cu
0.91Zn
0.09The S sample has and similar flower-like structure of ZnS and particle diameter branch.
Embodiment 4: flower-shaped binary sulfide Cu
0.93Zn
0.07The preparation of S particulate.
The ZnS that is selected for use among the ZnS that present embodiment is selected for use and the embodiment 1 is identical.
Choose have flower-like structure the ZnS material as precursor; Place the ZnS powder of 2.924g among the neutralized verdigris solution of 15mL2mol/L, reaction is 120 minutes under room temperature, uses concentration washing 5 times with Hydrogen chloride as 3mol/L; Deionized water wash 2 times; Spinning afterwards, resulting solids promptly obtains consisting of Cu in 50 ℃ of dryings 20 hours
0.93Zn
0.07The flower-shaped binary sulfide of S.
Product after handling through the Cu salts solution can spectrogram shown in Fig. 3 d.
Product after handling through the Cu salts solution can spectrogram shown in Fig. 3 d; The characteristic peak of existing Zn wherein; Also have the characteristic peak of Cu to occur, and the characteristic peak of Cu is very strong, shows that homo-ion in the solution with the zinc element in the solid ZnS particle permutoid reaction taken place really.Quantitative power spectrum calculation result shows, Cu in this sample: Zn (mol ratio)=13.3: 1, and then the molecular formula of sample can be write Cu
0.93Zn
0.07S.Cu
0.93Zn
0.07The X-ray diffracting spectrum of S sample is shown in Fig. 1 e; Wherein in 2 θ=27.5,29.5,32,39.5,48,53, the diffraction peak at 59 places can be diffracted to the structure of α-ZnS (JCPDS 1-677); But there is skew the position of its diffraction peak slightly with initial thing ZnS, and the intensity of diffraction peak is also different.SEM figure shown in Fig. 2 e shows Cu
0.93Zn
0.07The S sample has and similar flower-like structure of ZnS and particle diameter branch.
Embodiment 5: flower-shaped binary sulfide Cu
0.95Zn
0.05The preparation of S particulate.
The ZnS that is selected for use among the ZnS that present embodiment is selected for use and the embodiment 1 is identical.
Choose have flower-like structure the ZnS material as precursor; Place the ZnS powder of 0.2924g the mixing solutions of neutralized verdigris solution of copper-bath and 23.5mL1mol/L of copper nitrate solution, the 10mL4mol/L of 20mL5mol/L, reaction is 180 minutes under room temperature, uses concentration to wash 5 times as the salpeter solution of 5mol/L; Deionized water wash 5 times; Spinning afterwards, resulting solids promptly obtains consisting of Cu in 65 ℃ of dryings 12 hours
0.95Zn
0.05The flower-shaped binary sulfide of S.
Product after handling through the Cu salts solution can spectrogram shown in Fig. 3 e; The characteristic peak of existing Zn wherein; Also have the characteristic peak of Cu to occur, and the characteristic peak of Cu is very strong, shows that homo-ion in the solution with the zinc element in the solid ZnS particle permutoid reaction taken place really.Quantitative power spectrum calculation result shows, Cu in this sample: Zn (mol ratio)=19: 1, and then the molecular formula of sample can be write Cu
0.95Zn
0.05S.CuCu
0.95Zn
0.05The X-ray diffracting spectrum of S sample is shown in Fig. 1 f; Wherein in 2 θ=27.5,29.5,32,39.5,48,53, the diffraction peak at 59 places can be diffracted to the structure of α-ZnS (JCPDS 1-677); But there is skew the position of its diffraction peak slightly with initial thing ZnS, and the intensity of diffraction peak is also different.SEM figure shown in Fig. 2 f shows Cu
0.95Zn
0.05The S sample has and similar flower-like structure of ZnS and particle diameter branch.
Result among above-mentioned each embodiment all shows, adopts cationic exchange method described in this patent effectively to prepare and has the adjustable binary sulfide Cu of the controlled composition of pattern
XZn
1-XThe S particulate, and this method is simple, quick, easy handling.
Claims (6)
1. binary sulfide Cu with flower-like structure
XZn
1-XThe S particulate is characterized in that: its particle appearance is flower-shaped, consists of the sulfide that two kinds of metal centers constitute, and its molecular formula is Cu
XZn
1-XS, the span of X is 0.85～0.95 in the formula.
2. the binary sulfide Cu with flower-like structure according to claim 1
XZn
1-XThe S particulate is characterized in that: described binary sulfide Cu
XZn
1-XThe particle size range of S particulate is 100nm～20 μ m.
3. claim 1 or 2 described binary sulfide Cu with flower-like structure
XZn
1-XThe preparation method of S particulate comprises the steps:
(1) flower-shaped micrometer structure ZnS's is synthetic: accurately take by weighing 0.4561 gram forerunner title complex Zn (phen)
2(H2O)
2]
2L6H
2In O to 50 milliliter the triangular flask, the adjacent phenanthroline of phen=; The L=p-methyl benzenesulfonic acid adds 11 milliliters of terepthaloyl moietie, is stirred to the title complex presoma and dissolves fully; Then accurately take by weighing 0.0381 gram thiocarbamide again, be dissolved in 5 milliliters of anhydrous ethylenediamines; The ethylenediamine solution that will be dissolved with thiocarbamide then slowly is added drop-wise in forerunner's complex solution and goes, wait all thiourea solutions all to be added drop-wise to triangular flask after, continue to stir half hour again; At last above-mentioned solution being transferred to 23mL has in the stainless steel still of polytetrafluoroethylliner liner, and the stainless steel still is put into the constant temperature air dry oven; Heating is 24 hours under 125 degree; Take out the stainless steel still, open inner bag, pour out supernatant liquid, with deionized water and absolute ethanol washing deposition several, put into then vacuum drying oven 60 spend under freeze-day with constant temperature 4 hours, products therefrom is flower-shaped micrometer structure ZnS, yield is 83%;
The ZnS powder that (2) will have a flower-like structure joins in the middle of the aqueous solution of soluble copper salt that concentration is 0.01～5mol/L, and at room temperature with the magnetic stirrer reaction after 180 minutes, spinning obtains throw out;
(3) with the throw out that obtains with dilute acid soln washing 2～5 times, water washing 2～5 times in 50～80 ℃ of dryings 5～24 hours, promptly obtains having the binary sulfide Cu of flower-like structure
XZn
1-XThe S particulate.
4. the preparation method with binary sulfide of flower-like structure according to claim 3 is characterized in that: described size with ZnS powder of flower-like structure is 100nm～20 μ m.
5. according to claim 3 or 4 described binary sulfide Cu with flower-like structure
XZn
1-XThe preparation method of S particulate is characterized in that: described soluble copper salt is selected from the mixing of any one or two or more materials in copper sulfate, cupric nitrate, cupric chloride or the neutralized verdigris.
6. the binary sulfide Cu with flower-like structure according to claim 3
XZn
1-XThe preparation method of S particulate is characterized in that: described dilute acid soln is meant that concentration is a kind of in hydrochloric acid, sulfuric acid, nitric acid or the acetum of 0.1～5mol/L.
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| CN102698702A (en) * | 2012-06-18 | 2012-10-03 | 中国科学院福建物质结构研究所 | Zinc sulfide-based nano adsorption material and preparation method and application thereof |
| CN102795655B (en) * | 2012-07-30 | 2015-04-08 | 黑龙江大学 | Method for preparing hierarchical floriform hollow-structure CuS |
| CN105036175B (en) * | 2015-08-14 | 2017-03-22 | 新疆大学 | Method of preparing copper sulfide-zinc sulfide heterojunction three-dimensional nanostructure by using solid phase method |
| CN107500337B (en) * | 2017-07-13 | 2019-05-17 | 北京华腾新材料股份有限公司 | A kind of near infrared absorption heat shielding granules of pigments and preparation method |
| CN107469834B (en) * | 2017-08-25 | 2020-07-07 | 内江师范学院 | Preparation method of ZnS/CuS nanosheet composite photocatalyst |
| CN108107084A (en) * | 2017-12-11 | 2018-06-01 | 梁金凤 | A kind of gas detection cell based on ternary nano material |
| CN108273521A (en) * | 2018-03-26 | 2018-07-13 | 湘潭大学 | A kind of preparation method of the flower-shaped micron ball superstructure visible light catalyst of the copper sulfide zinc being made of nanometer sheet |
| CN114990584B (en) * | 2022-06-22 | 2023-04-04 | 江西八六三实业有限公司 | Preparation method of copper-based catalyst for electrochemical reduction of carbon dioxide |
| CN115518658B (en) * | 2022-09-20 | 2023-06-20 | 广州大学 | Preparation method and application of flower cluster spherical multiphase Fenton catalyst |
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| Jin’an Zhao et al.Cation Exchange Induced Tunable Properties of a Nanoporous Octanuclear Cu(II) Wheel with Double-Helical Structure.《J. AM. CHEM. SOC》.2008,第130卷第15222-15223页. * |
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