CN102161477B - Method for preparing copper zinc tin selenium nanoparticles through aqueous phase synthesis - Google Patents
Method for preparing copper zinc tin selenium nanoparticles through aqueous phase synthesis Download PDFInfo
- Publication number
- CN102161477B CN102161477B CN 201110094002 CN201110094002A CN102161477B CN 102161477 B CN102161477 B CN 102161477B CN 201110094002 CN201110094002 CN 201110094002 CN 201110094002 A CN201110094002 A CN 201110094002A CN 102161477 B CN102161477 B CN 102161477B
- Authority
- CN
- China
- Prior art keywords
- zinc
- tin
- copper
- nano particle
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a method for preparing copper zinc tin selenium nanoparticles through aqueous phase synthesis and belongs to the technical field of preparation of inorganic nano materials. In the method, the copper zinc tin selenium nanoparticles are prepared in an aqueous phase by using sulfydryl carboxylic acid as a protective agent; and the obtained nanoparticles can be dispersed into water or glycol. The method is reasonable in design, simple in operation, controllable in reaction, high in repeatability and easy in large-scale production. The obtained copper zinc tin selenium nanoparticles can be dispersed into water or glycol to serve as nano ink and are applied in the fields of solar batteries, electronic industry and the like.
Description
Technical field
The present invention relates to the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water, belong to the inorganic nano material preparing technical field.
Background technology
Sun power is primary energy source, is again renewable energy source, and aboundresources does not have any pollution to environment.Solving the key of current energy problem, is exactly how further to develop sun power.Solar cell is one of emphasis of sun power utilization.In recent years, copper-zinc-tin-sulfur (CZTS) and copper-zinc-tin-selenium (CZTSe) semiconductor material do not contain hypertoxic elements such as cadmium, arsenic because the element reserves are abundant, receive extensive concern, have become the brand-new material of thin-film solar cells.
Using the dispersive nanometer particle ink is a kind of manufacturing solar cells novel process.Be dispersed in CZTSe nano particle in the organic phase by wide coverage.Chinese patent file CN101700873A (200910310115.X) discloses a kind of preparation method of copper-zinc-tin-selenium nanoparticles; This method selects for use oleyl amine to make solvent; With divalent zinc salt, divalence or tetravalence pink salt, monovalence or cupric salt and selenium powder with (1~2.2): (1~1.2): (2~2.2): the mol ratio of (4~8.8) adds oleyl amine, obtains copper-zinc-tin-selenium nanoparticles after the thermal treatment.Chinese patent file CN101885071A (201010185891.4) discloses a kind of preparation method of copper-zinc-tin-selenium nano powder material; The alkyl alcoholamine that this method selects for use boiling point to be not less than 180 ℃ is made solvent; According to Cu: Zn: Sn=2: 1: 1 mol ratio prepares the alkyl alcoholamine solution (system A) of Cu, Zn and Sn; The alkyl alcoholamine solution (system B) for preparing Se simultaneously; Then according to Se: Cu=2: 1 mixed in molar ratio system A and system B, stirring, heating reflux reaction obtain copper-zinc-tin-selenium nano body material under the protection of inert gas condition.But the nano particle of above method preparation uses high boiling organic solvent and protective material in a large number; Easy carbonization is difficult to remove when thermal treatment; Be prone to form the deathnium, when the copper-zinc-tin-selenium (CZTSe) of this method preparation is used as semiconductor material to a great extent limit the transformation efficiency of solar cell.
Summary of the invention
To the deficiency of prior art, the present invention provides the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water.
Technical scheme of the present invention is following:
The preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water, step is following:
1) mantoquita, zinc salt, pink salt are pressed (1~2): (0.5~5): the mol ratio of (0.5~1) is soluble in water, is made into the solution of 0.05~0.15mol/L, adds the protective material of 1~20 times of metal-salt total mole number again, stirs down and transfers PH to 12~13 with alkali, gets solution A.
2) add 0.01-1mol/L seleno sodium sulfite aqueous solution, the volume ratio 1 of solution A and 0.01-1mol/L seleno sodium sulfite aqueous solution in the solution A that step 1) makes: (1~4), stirred refluxed 0.5-24 hour.
3) after step 2) reaction finishes; Be cooled to room temperature, spinning then, gained deposition is with ethanol or acetone 3-5 time; Throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in water or the terepthaloyl moietie again.
" being made into the solution of 0.05~0.15mol/L " described in the step 1), mol wherein is meant the total mole number of metal-salt.
Preferably, the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water, step is following:
1) mantoquita, zinc salt, pink salt are pressed (1~2): (1~4): the mol ratio of (0.5~1) is soluble in water, is made into the solution of 0.1mol/L, adds the protective material of 1~20 times of metal-salt total mole number again, stirs down and transfers PH to 12~13 with alkali, gets solution A.
2) in the solution A that step 1) makes, add 1: 1 0.1mol/L seleno sodium sulfite aqueous solution of volume ratio, under agitation refluxed 2-10 hour.
3) after step 2) reaction finishes; Be cooled to room temperature, spinning then, gained deposition is with ethanol or acetone 3-5 time; Throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in water or the terepthaloyl moietie again.
The described mantoquita of said step 1) is a kind of in cupric chloride, cupric nitrate, venus crystals, copper sulfate, the cupric perchlorate.
The described pink salt of said step 1) is a kind of in tin protochloride, stannous sulfate, the tin tetrachloride.
The described zinc salt of said step 1) is a kind of in zinc chloride, zinc nitrate, zinc acetate, zinc sulfate, zinc perchlorate, the zn phosphate.
The described protective material of said step 1) is a Thiovanic acid, thiohydracrylic acid, dimercaptosuccinic acid, one or more mixing in the succimer.
The described alkali of said step 1) is ammoniacal liquor, sodium hydroxide, Pottasium Hydroxide, quadrol, one or more mixing in the triethylamine.
Further preferred, the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water, step is following:
1) takes by weighing 4 mmole cupric chlorides, 3 mmole zinc chloride, 3 mmole tin chlorides, be dissolved in 100 ml waters, add 10 mmole dimercaptosuccinic acids, regulate PH to 13, stir and make its dispersion, get solution A with sodium hydroxide.
2) in the solution A that step 1) makes, add 100 milliliters of 0.1mol/L seleno sodium sulfite aqueous solutions, under agitation refluxed 10 hours.
3) after step 2) reaction finishes, be cooled to room temperature, spinning then, the gained deposition is cleaned 3 times with ethanol, and the throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in water or the terepthaloyl moietie again.
Another kind of preferred version is following:
1) takes by weighing 1 mmole cupric chloride, 3.5 mmole zinc chloride, 0.5 mmole tin chloride, be dissolved in 50 ml waters, add 72 mmole Thiovanic acids, regulate PH to 12, stir and make its dispersion, get solution A with ammoniacal liquor.
2) in the solution A that step 1) makes, add 50 milliliters of 0.1mol/L seleno sodium sulfite aqueous solutions, under agitation refluxed 2 hours.
3) after step 2) reaction finishes, be cooled to room temperature, spinning then, the gained deposition is cleaned 5 times with ethanol, and the throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in the water again.
The thing of the copper-zinc-tin-selenium nano particle of the present invention's preparation is mutually through X-ray diffraction spectrum (XRD) test, and adopting Bruker D8X-x ray diffractometer x is that diffraction light sources is made X light diffracting analysis to product with Cu-K alpha-ray (wavelength X=1.54178
).
The pattern of the copper-zinc-tin-selenium nano particle of the present invention's preparation shows through transmission electron microscope photo (TEM), adopts JEM-1011 (acceleration voltage: 100KV) transmission electron microscope.
Compared with prior art, the present invention has following usefulness: the present invention uses antivacuum chemical process, at the synthetic copper-zinc-tin-selenium nano particle of aqueous phase; Do not need expensive equipment, do not need organic solvent, the protective material of use (200 degrees centigrade) at low temperatures decomposes; Be easy to remove; It is residual that carbonization does not at high temperature form carbon, and the nano particle that obtains can be dispersed in water or the terepthaloyl moietie, can be steady in a long-term at ambient temperature.Method is simple, and is with low cost, and very high environment friendly is arranged, and is convenient to scale operation.
Description of drawings
Fig. 1 is the X-ray diffraction spectrum (XRD) of the copper-zinc-tin-selenium nano particle of the embodiment of the invention 1 preparation;
Fig. 2 is the transmission electron microscope photo (TEM) of the copper-zinc-tin-selenium nano particle of the embodiment of the invention 1 preparation;
Fig. 3 is the X-ray diffraction spectrum (XRD) of the copper-zinc-tin-selenium nano particle of the embodiment of the invention 2 preparations;
Fig. 4 is the transmission electron microscope photo (TEM) of the copper-zinc-tin-selenium nano particle of the embodiment of the invention 2 preparations;
Embodiment
Below in conjunction with embodiment the present invention is further specified, but be not limited thereto.
Used raw material is commercial product in the embodiment of the invention, and purity is analytical pure.
The thing of the copper-zinc-tin-selenium nano particle of the present invention's preparation is mutually through X-ray diffraction spectrum (XRD) test, and adopting Bruker D8X-x ray diffractometer x is that diffraction light sources is made X light diffracting analysis to product with Cu-K alpha-ray (wavelength X=1.54178
).
The pattern of the copper-zinc-tin-selenium nano particle of the present invention's preparation shows through transmission electron microscope photo (TEM), adopts the JEM-2100 transmission electron microscope.
Embodiment 1: the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water, and step is following:
1) takes by weighing 4 mmole cupric chlorides, 3 mmole zinc chloride, 3 mmole tin chlorides, be dissolved in 100 ml waters, add 10 mmole dimercaptosuccinic acids, regulate PH to 13, stir and make its dispersion, get solution A with sodium hydroxide.
2) in the solution A that step 1) makes, add 100 milliliters of 0.1mol/L seleno sodium sulfite aqueous solutions, under agitation refluxed 10 hours.
3) after step 2) reaction finishes, be cooled to room temperature, spinning then, the gained deposition is cleaned 3 times with ethanol, and the throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in water or the terepthaloyl moietie again.
Embodiment 2: the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water, and step is following:
1) takes by weighing 1 mmole cupric chloride, 3.5 mmole zinc chloride, 0.5 mmole tin chloride, be dissolved in 50 ml waters, add 72 mmole Thiovanic acids, regulate PH to 12, stir and make its dispersion, get solution A with ammoniacal liquor.
2) in the solution A that step 1) makes, add 50 milliliters of 0.1mol/L seleno sodium sulfite aqueous solutions, under agitation refluxed 2 hours.
3) after step 2) reaction finishes, be cooled to room temperature, spinning then, the gained deposition is cleaned 5 times with ethanol, and the throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in the water again.
Embodiment 3: of embodiment 1, different is to replace cupric chloride with cupric nitrate.
Embodiment 4: of embodiment 1, different is to replace cupric chloride with copper sulfate.
Embodiment 5: of embodiment 1, different is to replace tin protochloride with stannous sulfate.
Embodiment 6: of embodiment 1, different is to replace tin protochloride with tin tetrachloride.
Embodiment 7: of embodiment 1, different is to replace zinc chloride with zinc nitrate.
Embodiment 8: of embodiment 1, different is to replace zinc chloride with zinc acetate.
Embodiment 9: of embodiment 1, different is to replace dimercaptosuccinic acid with Thiovanic acid.
Embodiment 10: of embodiment 1, different is to replace dimercaptosuccinic acid with thiohydracrylic acid.
Embodiment 11: of embodiment 1, different is to replace dimercaptosuccinic acid with succimer.
Embodiment 12: of embodiment 1, different is to use aqueous ammonia to replace sodium hydroxide.
Embodiment 13: of embodiment 1, different is to replace sodium hydroxide with quadrol.
Embodiment 14: of embodiment 2, different is to replace Thiovanic acid with succimer.
Embodiment 15: of embodiment 2, different is to replace Thiovanic acid with dimercaptosuccinic acid.
Embodiment 16: of embodiment 2, different is to replace Thiovanic acid with thiohydracrylic acid.
Embodiment 17: the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water, and step is following:
1) takes by weighing 0.4 mmole cupric chloride, 0.3 mmole zinc chloride, 0.3 mmole tin chloride, be dissolved in 10 ml waters, add 1 mmole dimercaptosuccinic acid, regulate PH to 13, stir and make its dispersion, get solution A with sodium hydroxide.
2) in the solution A that step 1) makes, add 10 milliliters of 0.1mol/L seleno sodium sulfite aqueous solutions, under agitation refluxed 10 hours.
3) after step 2) reaction finishes, be cooled to room temperature, spinning then, the gained deposition is cleaned 5 times with ethanol, and the throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in the terepthaloyl moietie again.
Embodiment 18: the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water, and step is following:
1) takes by weighing 20 mmole cupric chlorides, 10 mmole zinc chloride, 10 mmole tin chlorides, be dissolved in 400 ml waters, add 40 mmole dimercaptosuccinic acids, regulate PH to 13, stir and make its dispersion, get solution A with sodium hydroxide.
2) in the solution A that step 1) makes, add 400 milliliters of 0.1mol/L seleno sodium sulfite aqueous solutions, under agitation refluxed 10 hours.
3) after step 2) reaction finishes, be cooled to room temperature, spinning then, the gained deposition is cleaned 5 times with ethanol, and the throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in the terepthaloyl moietie again.
Claims (8)
1. the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a water, step is following:
1) mantoquita, zinc salt, pink salt are pressed (1~2): (0.5~5): the mol ratio of (0.5~1) is soluble in water; The total mol concentration that is made into metal-salt is the solution of 0.05~0.15mol/L; The protective material that adds 1~20 times of metal-salt total mole number again; With adjusting PH with base to 12~13, get solution A under stirring; Described protective material is a Thiovanic acid, thiohydracrylic acid, dimercaptosuccinic acid, one or more mixing in the succimer;
2) add 0.01-1mol/L seleno sodium sulfite aqueous solution, the volume ratio 1 of solution A and 0.01-1mol/L seleno sodium sulfite aqueous solution in the solution A that step 1) makes: (1~4), stirred refluxed 0.5-24 hour;
3) after step 2) reaction finishes; Be cooled to room temperature, spinning then, gained deposition is with ethanol or acetone 3-5 time; Throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in water or the terepthaloyl moietie again.
2. the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water as claimed in claim 1, step is following:
1) mantoquita, zinc salt, pink salt are pressed (1~2): (1~4): the mol ratio of (0.5~1) is soluble in water; The total mol concentration that is made into metal-salt is the solution of 0.1mol/L; The protective material that adds 1~20 times of metal-salt total mole number again with adjusting PH with base to 12~13, gets solution A under stirring;
2) the 0.1mol/L seleno sodium sulfite aqueous solution of adding volume ratio 1:1 in the solution A that step 1) makes under agitation refluxed 2-10 hour;
3) after step 2) reaction finishes; Be cooled to room temperature, spinning then, gained deposition is with ethanol or acetone 3-5 time; Throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in water or the terepthaloyl moietie again.
3. according to claim 1 or claim 2 the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water is characterized in that, the described mantoquita of step 1) is a kind of in cupric chloride, cupric nitrate, venus crystals, copper sulfate, the cupric perchlorate.
4. according to claim 1 or claim 2 the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water is characterized in that, the described pink salt of step 1) is a kind of in tin protochloride, stannous sulfate, the tin tetrachloride.
5. according to claim 1 or claim 2 the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water is characterized in that, the described zinc salt of step 1) is a kind of in zinc chloride, zinc nitrate, zinc acetate, zinc sulfate, zinc perchlorate, the zn phosphate.
6. according to claim 1 or claim 2 the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water is characterized in that the described alkali of step 1) is ammoniacal liquor, sodium hydroxide, Pottasium Hydroxide, quadrol, one or more mixing in the triethylamine.
7. according to claim 1 or claim 2 the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water is characterized in that step is following:
1) takes by weighing 4 mmole cupric chlorides, 3 mmole zinc chloride, 3 mmole tin chlorides, be dissolved in 100 ml waters, add 10 mmole dimercaptosuccinic acids, regulate pH to 13, stir and make its dispersion, get solution A with sodium hydroxide;
2) in the solution A that step 1) makes, add 100 milliliters of 0.1mol/L seleno sodium sulfite aqueous solutions, under agitation refluxed 10 hours;
3) after step 2) reaction finishes, be cooled to room temperature, spinning then, the gained deposition is cleaned 3 times with ethanol, and the throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in water or the terepthaloyl moietie again.
8. according to claim 1 or claim 2 the preparation method of the synthetic copper-zinc-tin-selenium nano particle of a kind of water is characterized in that step is following:
1) takes by weighing 1 mmole cupric chloride, 3.5 mmole zinc chloride, 0.5 mmole tin chloride, be dissolved in 50 ml waters, add 72 mmole Thiovanic acids, regulate pH to 12, stir and make its dispersion, get solution A with ammoniacal liquor;
2) in the solution A that step 1) makes, add 50 milliliters of 0.1mol/L seleno sodium sulfite aqueous solutions, under agitation refluxed 2 hours;
3) after step 2) reaction finishes, be cooled to room temperature, spinning then, the gained deposition is cleaned 5 times with ethanol, and the throw out after the cleaning is the copper-zinc-tin-selenium nano particle that makes, and this copper-zinc-tin-selenium nano particle can be dispersed in the water again.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110094002 CN102161477B (en) | 2011-04-14 | 2011-04-14 | Method for preparing copper zinc tin selenium nanoparticles through aqueous phase synthesis |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110094002 CN102161477B (en) | 2011-04-14 | 2011-04-14 | Method for preparing copper zinc tin selenium nanoparticles through aqueous phase synthesis |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102161477A CN102161477A (en) | 2011-08-24 |
CN102161477B true CN102161477B (en) | 2012-12-19 |
Family
ID=44462980
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 201110094002 Expired - Fee Related CN102161477B (en) | 2011-04-14 | 2011-04-14 | Method for preparing copper zinc tin selenium nanoparticles through aqueous phase synthesis |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102161477B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102627315B (en) * | 2012-04-25 | 2014-03-12 | 桂林理工大学 | Preparation method of wurtzite structure CZTS (Se) system powder |
CN102732095B (en) * | 2012-07-05 | 2014-01-15 | 单联臣 | Nano-ink, and preparation and application thereof |
CN102849685B (en) * | 2012-08-16 | 2014-07-30 | 中国科学院合肥物质科学研究院 | Method for synthesis of band gap-adjustable monodispersed Cu2ZnSn(S1-xSex)4 nano-crystals by crystal phase control |
EP3523248A1 (en) * | 2016-10-07 | 2019-08-14 | Haldor Topsøe A/S | KESTERITE MATERIAL OF CZTS, CZTSe OR CZTSSe TYPE |
CN108706558A (en) * | 2018-06-12 | 2018-10-26 | 桂林理工大学 | A kind of preparation method in eight selenium of copper-based upper growth, four bronze medal, one potassium micron linear array |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101700873A (en) * | 2009-11-20 | 2010-05-05 | 上海交通大学 | Preparation method of copper-zinc-tin-selenium nanoparticles |
CN101885071A (en) * | 2010-05-28 | 2010-11-17 | 电子科技大学 | Method for preparing copper-zinc-tin-selenium nano powder material |
-
2011
- 2011-04-14 CN CN 201110094002 patent/CN102161477B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101700873A (en) * | 2009-11-20 | 2010-05-05 | 上海交通大学 | Preparation method of copper-zinc-tin-selenium nanoparticles |
CN101885071A (en) * | 2010-05-28 | 2010-11-17 | 电子科技大学 | Method for preparing copper-zinc-tin-selenium nano powder material |
Non-Patent Citations (1)
Title |
---|
Pengcheng Dai et al..Band-gap tunable (Cu2Sn)x/3Zn1-xS nanoparticles for solar cells.《Chem. Commun.》.2010,第46卷5749–5751. * |
Also Published As
Publication number | Publication date |
---|---|
CN102161477A (en) | 2011-08-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Huang et al. | ZnxCd1-xS based materials for photocatalytic hydrogen evolution, pollutants degradation and carbon dioxide reduction | |
CN102254985B (en) | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material | |
CN102010004B (en) | Method for preparing vanadium disulphide nano powder | |
CN102161477B (en) | Method for preparing copper zinc tin selenium nanoparticles through aqueous phase synthesis | |
CN102633297A (en) | Preparation method of general-purpose multi-metal sulfide nano-material | |
CN111420664B (en) | Preparation method of flaky cuprous oxide/cobaltous oxide nanocomposite and application of flaky cuprous oxide/cobaltous oxide nanocomposite in catalyzing ammonia borane hydrolysis hydrogen production | |
CN102502788A (en) | Simple and controllable preparation method of copper-indium-sulfur ternary semiconductor nano granules | |
Xia et al. | A nontoxic and low-cost hydrothermal route for synthesis of hierarchical Cu 2 ZnSnS 4 particles | |
CN102633309A (en) | Hydrothermal preparation method for NiS2 with controllable shape | |
CN103073073A (en) | Synthetic method of transition metal sulfide | |
CN107138167B (en) | A kind of preparation method of the multiphase hetero-junctions Nano cadmium sulphide of special appearance | |
CN102249289A (en) | Method for preparing spiauterite ZnS fine nanorod with solvothermal method | |
CN104817120A (en) | Preparation method of sea urchin-like Ni/Co composite basic carbonate | |
CN111790412B (en) | Method for producing carbon compound by reducing carbon dioxide | |
CN103213956A (en) | Preparation method of CuInSe2 with a chalcopyrite structure and CuIn1-xGazSe2 nano particles | |
CN102079541B (en) | Method for preparing doping type hexagonal system nano ZnS at low temperature | |
CN101857265A (en) | Method for preparing metal sulfide nanocrystalline | |
CN102631919A (en) | Preparation method of copper-titanium-oxide mesomorphism material | |
CN102897722B (en) | Alpha-In2Se3 nano-grade flower-ball solvothermal synthesizing method | |
CN111111699A (en) | Nickel-cobalt disulfide composite material and preparation method and application thereof | |
CN107570180B (en) | Method for preparing tin disulfide/bismuth oxyiodide composite photocatalyst by solvothermal method | |
Shele et al. | Solvothermal synthesis and properties of three antimony chalcogenides containing transition metal zinc | |
CN103058259A (en) | Preparation method for chestnut-shaped copper sulphide hollow micron sphere composed of nanosheets | |
CN102897723A (en) | Hydrothermal method for preparing selenium-copper-based nano-crystals | |
CN109273289A (en) | Solvent method prepares Ni-based cobalt acid magnesium base composite material and its application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121219 Termination date: 20180414 |