CN102267714A - Preparation method for hollow silk cocoon-like CuO nanomaterial - Google Patents
Preparation method for hollow silk cocoon-like CuO nanomaterial Download PDFInfo
- Publication number
- CN102267714A CN102267714A CN2010101973787A CN201010197378A CN102267714A CN 102267714 A CN102267714 A CN 102267714A CN 2010101973787 A CN2010101973787 A CN 2010101973787A CN 201010197378 A CN201010197378 A CN 201010197378A CN 102267714 A CN102267714 A CN 102267714A
- Authority
- CN
- China
- Prior art keywords
- silk cocoon
- hollow
- cuo
- solution
- hollow silk
- 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.)
- Granted
Links
Images
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a preparation method for a hollow silk cocoon-like CuO nanomaterial, and provides a new method for the preparation technology of a hollow CuO nanomaterial. According to the present invention, the disadvantages in the prior art are overcome. The method is characterized in that: a normal-pressure and one-step microwave chemical synthesis method is adopted for preparing a hollow silk cocoon-like CuO nanomaterial, ie., aqueous solutions of soluble copper salt such as copper acetate and the like, and a queous solution of urea are adopted as precursor solutions, a one-step microwave irradiation process is adopted to prepare the hollow silk cocoon-like CuO nanomaterial. The hollow silk cocoon-like CuO nanomaterial provided by the present invention is ellipsoidal, and has characteristics of similar silk cocoon morphology, hollow structure, no agglomeration, monodisperse, and long diameter between 250-400 nm. With the present invention, the method has simple process; any surfactant and organic solvent is not used; the process is clean and environment-friendly; the method has characteristics of low reaction temperature, short reaction time, energy saving, low carbon, high performance, easy and available raw materials, low cost, and is applicable for the industrial production; the prepared material can be applicable for the fields of catalysis, antibacterial, solar battery, sensor material and the like.
Description
Technical field
The invention belongs to the semiconductor nano material preparing technical field, specifically, relate to a kind of hollow silk cocoon shape CuO preparation of nanomaterials.
Background technology
Nano material all has important effect because of its functions peculiar and character at numerous areas such as nanometer light, electricity, magnetic.The performance of nano material depends on its appearance structure and size of particles, and therefore the nano material of the synthetic unique appearance structure of control more and more is subjected to people's great attention.The nano material of hollow structure is one of investigation of materials focus and difficult point because of having bigger specific surface area, lower density, good perviousness and unique photoelectricity and surface property always.
CuO is good semiconductor material, all has a wide range of applications at aspects such as photo-thermal, photoelectricity, transmitter, superconduction, solar cell, Li-Ion rechargeable battery and organic catalyst compounds.Again because the special character such as optics, electricity, magnetics and catalysis of hollow nanostructures may have great importance the preparation and the research of hollow CuO nanostructure.The report of the synthetic method of hollow CuO nanostructure also is not a lot of at present.The S Y Gao of He'nan Normal University etc. has reported copper sulfate solution has been joined in the ammonia soln that contains tyrosine, fully stirring the back reacted 4 hours at 130 ℃ by hydrothermal method, made outside diameter that the nanometer sheet by the about 250nm of diameter assembles micro-sphere structure between the inner hollow of 1.5～3 μ m, tyrosine plays a part surfactant-like agent (Shuyan Gao, Shuxia Yang, Jie Shu, et al., Green Fabrication of HierarchicalCuO Hollow Micro/Nanostructures and Enhanced Performance as Electrode Materials forLithium-ion Batteries[J], J.Phys.Chem.C, 2008,112:19324-19328.).The S L Wang of Institutes Of Technology Of Zhejiang etc. has reported that with cetyl trimethylammonium bromide (CTAB) be tensio-active agent, obtained the hollow micron spherical structure (ShunliWang of outside diameter 5～10 μ m that assemble by nano strip in 6 hours 180 ℃ of reactions by hydrothermal method with the aqueous solution of cupric nitrate and urea, Hui Xu, Liuqin Qian, et al., CTAB-assisted synthesis and photocatalytic property of CuOhollow microspheres[J], J.Solid State Chem., 2009,182:1088-1093.).The Y G Zhang of Chinese University of Science and Technology etc. are raw material with neutralized verdigris and hexamethylenetetramine, at room temperature react earlier to make flaky title complex presoma ([Cu (C in 1 day
6H
12N
4)
2] (OOCCH
3)
2), obtained the diameter that assembles by nano particle hollow ball structure (Yange Zhang in 18 hours 180 ℃ of reactions by hydrothermal method again at 1～1.5 μ m, Shutao Wang, Titai Qiang, et al., Complexing-reagent assisted synthesis of hollow microspheres[J], Solid State Sciences, 2006,8:462-466.).The Zhu Jun of Shanghai Communications University etc. has reported soluble copper salt (neutralized verdigris, cupric nitrate or copper sulfate) aqueous solution and ammoniacal liquor is mixed with clarifying ammoniacal copper complex ion solution, add water-fast Fatty Alcohol(C12-C14 and C12-C18) (propyl carbinol then, n-hexyl alcohol, n-Octanol, butyleneglycol or glycerol), add tensio-active agent (sodium lauryl sulphate again, cetyl trimethylammonium bromide or song draw ketone) do the morphology control agent, adopt the microwave exposure technology, controlled microwave power is 300～1000W, reaction times is 1～3 minute, made by nanometer sheet and assembled nano-hollow sphere structured (a kind of hollow multilevel Cu O preparation of nanomaterials of CuO, Chinese invention patent, publication number: CN 101306832A).More than related preparation method, or need to use tensio-active agent, both increased preparation cost, also influence the purity and the output of product; Preparation process is loaded down with trivial details, temperature of reaction height (all be higher than 100 ℃, very the person is up to 180 ℃), and long reaction time (a few hours or tens hours) is unfavorable for industrialization production; And the prepared CuO hollow ball structure particle diameter that goes out is all bigger, and outside diameter all reaches micron order, and very the person is tens of microns, and quality is not high.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of hollow silk cocoon shape CuO preparation of nanomaterials is provided, technology is simple, raw material is easy to get, with low cost, operate controlled, simple and direct efficient, low-carbon environment-friendly, prepared nano material can be used for fields such as catalysis, antibiotic, solar cell and sensor material.
The objective of the invention is to realize by following technical solution.
Technical scheme of the present invention is to adopt a step microwave heating method to prepare hollow silk cocoon shape CuO nano material, that is, be raw material with soluble copper salt, deionized water and urea, gets precursor solution after stirring and dissolving, and the reaction of precursor solution heated by microwave is generated.Its concrete processing step is as follows:
(1) takes by weighing soluble copper salts such as 1mmol neutralized verdigris and be mixed with solution A with deionized water;
(2) take by weighing certain amount of urea and be mixed with solution B with deionized water, the mol ratio of mantoquita and urea is 1: 1～1: 3;
(3) under stirring state, solution A is joined in the solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed the microwave generator microwave exposure 20～40 minutes, temperature of reaction is 80 ± 10 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 changes;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed baking oven heated 6～12 hours, temperature is 40～60 ℃, collects black product and promptly obtains hollow silk cocoon shape CuO nano material of the present invention.
In the technique scheme, described hollow silk cocoon shape CuO nano material is elliposoidal, pattern is similar to silk cocoon, be hollow structure, do not have reunion, the single dispersion, long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, the hollow silk cocoon is assembled by more tiny nanoparticle, and the particle diameter of nanoparticle is between 5～20nm.
Soluble copper salt in the described step (1) comprises neutralized verdigris, cupric nitrate, cupric chloride and copper sulfate.
The mantoquita in the described step (2) and the mol ratio of urea are 1: 2.
Microwave irradiation time in the described step (4) is 30 minutes, and temperature of reaction is 80 ℃.
Described preparation technology's equipment is simple, and envrionment temperature is low, and is easy and simple to handle, good reproducibility; Do not adopt organic solvent and tensio-active agent to do template, the environmental friendliness cleaning; With short production cycle, productive rate is high, raw material sources are extensive, and are with low cost, suitability for industrialized production.
Compare with existing technology, beneficial effect of the present invention is embodied in:
(1) the present invention has adopted the method for no template to prepare hollow CuO nanostructure.
(2) the inventive method adopts the microwave exposure technology, can improve the crystallization velocity of product on the one hand, and operation steps is simple on the other hand, is swift in response control easily, high-efficiency environment friendly.
(3) the inventive method is with respect to reported method, and present method reaction conditions requires to realize easily to temperature, raw material etc., and is with low cost, can be directly under normal pressure through obtaining hollow CuO nanostructure once the step liquid phase cracking process.
Description of drawings
Fig. 1 is low power scanning electronic microscope (SEM) photo of the embodiment of the invention 1 hollow silk cocoon shape CuO nano material;
Fig. 2 is high power scanning electronic microscope (SEM) photo of the embodiment of the invention 1 hollow silk cocoon shape CuO nano material.
Embodiment
Below technical scheme of the present invention is done the description of further detailed complete by specific embodiment.Following embodiment further specifies of the present invention, and does not limit the scope of the invention.
Embodiment 1
Hollow silk cocoon shape CuO nano material of the present invention adopts a step microwave heating method to prepare, that is, be raw material with soluble copper salt, deionized water and urea, gets precursor solution after stirring and dissolving, and the reaction of precursor solution heated by microwave is generated.Its concrete processing step is as follows:
(1) takes by weighing the 0.1997g neutralized verdigris and be mixed with solution A with the 10mL deionized water;
(2) take by weighing 0.1203g urea and be mixed with solution B with the 50mL deionized water, the mol ratio of mantoquita and urea is 1: 2;
(3) under stirring state, solution A is joined in the solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed the microwave generator microwave exposure 30 minutes, temperature of reaction is 80 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 changes;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed baking oven heating 8 hours, temperature is 50 ℃, collects black product and promptly obtains hollow silk cocoon shape CuO nano material of the present invention.
Referring to accompanying drawing 1, low power field scan Electronic Speculum (SEM) photo of the hollow silk cocoon shape CuO nano material that makes by embodiment 1 described method.As can be seen from the figure hollow silk cocoon shape CuO nano material output height is elliposoidal, and pattern is similar to silk cocoon, and good dispersity does not have and reunites, and size distribution is even.
Referring to accompanying drawing 2, high power field scan Electronic Speculum (SEM) photo of the hollow silk cocoon shape CuO nano material that makes by embodiment 1 described method.As can be seen from the figure hollow silk cocoon shape CuO nano material is a hollow structure, and long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, and the hollow silk cocoon is assembled by more tiny nanoparticle, and the particle diameter of nanoparticle is between 5～20nm.
Embodiment 2
Hollow silk cocoon shape CuO nano material of the present invention adopts a step microwave heating method to prepare, that is, be raw material with soluble copper salt, deionized water and urea, gets precursor solution after stirring and dissolving, and the reaction of precursor solution heated by microwave is generated.Its concrete processing step is as follows:
(1) takes by weighing the 0.1999g neutralized verdigris and be mixed with solution A with the 10mL deionized water;
(2) take by weighing 0.0601g urea and be mixed with solution B with the 50mL deionized water, the mol ratio of mantoquita and urea is 1: 1;
(3) under stirring state, solution A is joined in the solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed the microwave generator microwave exposure 30 minutes, temperature of reaction is 80 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 changes;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed baking oven heating 10 hours, temperature is 50 ℃, collects black product and promptly obtains hollow silk cocoon shape CuO nano material of the present invention.
The CuO nano material that makes by embodiment 2 described methods is observed with SEM and to be elliposoidal, is hollow silk cocoon shape structure, and long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, is assembled by the nanoparticle of 5～20nm.
Embodiment 3
Hollow silk cocoon shape CuO nano material of the present invention adopts a step microwave heating method to prepare, that is, be raw material with soluble copper salt, deionized water and urea, gets precursor solution after stirring and dissolving, and the reaction of precursor solution heated by microwave is generated.
Its concrete processing step is as follows:
(1) takes by weighing the 0.1998g neutralized verdigris and be mixed with solution A with the 10mL deionized water;
(2) take by weighing 0.1802g urea and be mixed with solution B with the 50mL deionized water, the mol ratio of mantoquita and urea is 1: 3;
(3) under stirring state, solution A is joined in the solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed the microwave generator microwave exposure 30 minutes, temperature of reaction is 80 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 changes;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed baking oven heating 8 hours, temperature is 50 ℃, collects black product and promptly obtains hollow silk cocoon shape CuO nano material of the present invention.
The CuO nano material that makes by embodiment 3 described methods is observed with SEM and to be elliposoidal, is hollow silk cocoon shape structure, and long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, is assembled by the nanoparticle of 5～20nm.
Embodiment 4
Hollow silk cocoon shape CuO nano material of the present invention adopts a step microwave heating method to prepare, that is, be raw material with soluble copper salt, deionized water and urea, gets precursor solution after stirring and dissolving, and the reaction of precursor solution heated by microwave is generated.
Its concrete processing step is as follows:
(1) takes by weighing the 0.2416g cupric nitrate and be mixed with solution A with the 10mL deionized water;
(2) take by weighing 0.1202g urea and be mixed with solution B with the 50mL deionized water, the mol ratio of mantoquita and urea is 1: 2;
(3) under stirring state, solution A is joined in the solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed the microwave generator microwave exposure 30 minutes, temperature of reaction is 80 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 changes;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed baking oven heating 10 hours, temperature is 50 ℃, collects black product and promptly obtains hollow silk cocoon shape CuO nano material of the present invention.
The CuO nano material that makes by embodiment 4 described methods is observed with SEM and to be elliposoidal, is hollow silk cocoon shape structure, and long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, is assembled by the nanoparticle of 5～20nm.
Claims (5)
1. hollow silk cocoon shape CuO preparation of nanomaterials is characterized in that the concrete processing step of described method is as follows:
(1) takes by weighing soluble copper salts such as 1mmol neutralized verdigris and be mixed with solution A with deionized water;
(2) take by weighing certain amount of urea and be mixed with solution B with deionized water, the mol ratio of mantoquita and urea is 1: 1～1: 3;
(3) under stirring state, solution A is joined in the solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed the microwave generator microwave exposure 20～40 minutes, temperature of reaction is 80 ± 10 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 changes;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed baking oven heated 6～12 hours, temperature is 40～60 ℃, collects black product and promptly obtains hollow silk cocoon shape CuO nano material of the present invention.
2. a kind of hollow silk cocoon shape CuO preparation of nanomaterials according to claim 1, it is characterized in that, described hollow silk cocoon shape CuO nano material is elliposoidal, pattern is similar to silk cocoon, is hollow structure, does not have reunion, the single dispersion, long diameter is between 250～400nm, length diameter ratio is 1.2～1.5: 1, and the hollow silk cocoon is assembled by more tiny nanoparticle, and the particle diameter of nanoparticle is between 5～20nm.
3. a kind of hollow silk cocoon shape CuO preparation of nanomaterials according to claim 1 is characterized in that the soluble copper salt in the described step (1) comprises neutralized verdigris, cupric nitrate, cupric chloride and copper sulfate.
4. a kind of hollow silk cocoon shape CuO preparation of nanomaterials according to claim 1 is characterized in that the mantoquita in the described step (2) and the mol ratio of urea are 1: 2.
5. a kind of hollow silk cocoon shape CuO preparation of nanomaterials according to claim 1 is characterized in that the microwave irradiation time in the described step (4) is 30 minutes, and temperature of reaction is 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010197378 CN102267714B (en) | 2010-06-03 | 2010-06-03 | Preparation method for hollow silk cocoon-like CuO nanomaterial |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010197378 CN102267714B (en) | 2010-06-03 | 2010-06-03 | Preparation method for hollow silk cocoon-like CuO nanomaterial |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102267714A true CN102267714A (en) | 2011-12-07 |
| CN102267714B CN102267714B (en) | 2013-06-12 |
Family
ID=45050199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010197378 Expired - Fee Related CN102267714B (en) | 2010-06-03 | 2010-06-03 | Preparation method for hollow silk cocoon-like CuO nanomaterial |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102267714B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103373740A (en) * | 2012-04-20 | 2013-10-30 | 三星电机株式会社 | Method of producing a copper precursor and a copper precursor produced by using the same |
| CN105023762A (en) * | 2015-08-10 | 2015-11-04 | 安徽建筑大学 | Foliated CuO-NiO composite structure nano-material and preparation method thereof |
| CN106207148A (en) * | 2016-08-31 | 2016-12-07 | 青海中兴新能源有限公司 | A kind of preparation method of lithium ion battery negative material micro nano structure CuO |
| CN112647287A (en) * | 2020-12-17 | 2021-04-13 | 中国科学院过程工程研究所 | Super-hydrophobic material with hierarchical coarse structure and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101273723A (en) * | 2008-05-16 | 2008-10-01 | 曲阜师范大学 | Method for preparing nano copper oxide anti-bacteria agent |
| CN101407332A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Hydro-thermal synthesis method for cupric oxide nano-rod |
| JP2009132563A (en) * | 2007-11-30 | 2009-06-18 | Nagoya Institute Of Technology | Copper oxide powder material and method for morphological control thereof |
-
2010
- 2010-06-03 CN CN 201010197378 patent/CN102267714B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407332A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Hydro-thermal synthesis method for cupric oxide nano-rod |
| JP2009132563A (en) * | 2007-11-30 | 2009-06-18 | Nagoya Institute Of Technology | Copper oxide powder material and method for morphological control thereof |
| CN101273723A (en) * | 2008-05-16 | 2008-10-01 | 曲阜师范大学 | Method for preparing nano copper oxide anti-bacteria agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103373740A (en) * | 2012-04-20 | 2013-10-30 | 三星电机株式会社 | Method of producing a copper precursor and a copper precursor produced by using the same |
| KR101525651B1 (en) * | 2012-04-20 | 2015-06-03 | 삼성전기주식회사 | Method of manufacturing copper precursor and copper precursor manufactured by using the same |
| CN105023762A (en) * | 2015-08-10 | 2015-11-04 | 安徽建筑大学 | Foliated CuO-NiO composite structure nano-material and preparation method thereof |
| CN106207148A (en) * | 2016-08-31 | 2016-12-07 | 青海中兴新能源有限公司 | A kind of preparation method of lithium ion battery negative material micro nano structure CuO |
| CN112647287A (en) * | 2020-12-17 | 2021-04-13 | 中国科学院过程工程研究所 | Super-hydrophobic material with hierarchical coarse structure and preparation method and application thereof |
| CN112647287B (en) * | 2020-12-17 | 2022-01-04 | 中国科学院过程工程研究所 | Super-hydrophobic material with hierarchical coarse structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102267714B (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103663540B (en) | Simple preparation method of hollow spherical CuS nano material | |
| CN101920942B (en) | Method for controlling synthesis of zinc selenide multi-morphological nano material | |
| CN102125853B (en) | Nano zinc ferrite-graphene composite photocatalyst of visible light response and preparation method thereof | |
| CN100406117C (en) | Magnetic photocatalyst and its preparing method | |
| CN101549883B (en) | Method of preparing cuprous oxide rhombic dodecahedron and low-temperature reduction reaction | |
| CN105060351B (en) | Flower-like cobaltosic oxide material composed of nanoparticles and preparation method thereof | |
| CN104815637A (en) | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material | |
| CN108840313B (en) | Preparation method of multistage spherical nickel diselenide | |
| CN102515244B (en) | Hollow cuprous oxide nanometre material and preparation method for same | |
| CN103447549B (en) | Preparation method of cobalt nanosphere | |
| CN102267714B (en) | Preparation method for hollow silk cocoon-like CuO nanomaterial | |
| CN102491404A (en) | Copper oxide micro-nano composite structural material and preparation method thereof | |
| CN102179216B (en) | Method for preparing biomimetic alpha-Fe2O3/TiO2 nano composite material | |
| CN105502286A (en) | Preparation method of porous nano NiFe2O4 | |
| CN105521789A (en) | Preparation method of porous nano-scale BiFeO3 | |
| CN107827153B (en) | A kind of preparation method of nanometer of silver vanadate | |
| CN102001698B (en) | Preparation method of indium oxide mesoporous nanospheres | |
| CN101306833B (en) | Microwave method for preparing cadmium hydroxide nano materials | |
| CN104209126A (en) | Preparation method of bunchy prism cobaltosic oxide | |
| CN102877130B (en) | Preparation method of bismuth ferrite BiFeO3 monocrystal micrometer sheet | |
| CN102381725A (en) | Preparation method of hollow pumpkin-shaped CuO nano-material | |
| CN100560503C (en) | The preparation method of hollow multilevel copper oxide nano material | |
| CN101696028B (en) | Method for preparing zinc oxide nanocrystals between oil-water two-phase interfaces | |
| CN106219606A (en) | A kind of spherical Ag of nano flower3vO4preparation method | |
| CN105731518B (en) | Normal-temperature crystallization preparation method of octahedron cuprous oxide crystal |
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 | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 230601 Department of chemistry and materials engineering, Hefei University, 99 Jinxiu Road, Hefei, Anhui Patentee after: Hefei College Address before: 230022 No. 373, Mount Huangshan Road, Hefei, Anhui Patentee before: Hefei College |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130612 Termination date: 20140603 |
|
| EXPY | Termination of patent right or utility model |