CN103536625B - A kind of nanometer cerium oxide composite and preparation method thereof, antioxidant - Google Patents
A kind of nanometer cerium oxide composite and preparation method thereof, antioxidant Download PDFInfo
- Publication number
- CN103536625B CN103536625B CN201310452441.0A CN201310452441A CN103536625B CN 103536625 B CN103536625 B CN 103536625B CN 201310452441 A CN201310452441 A CN 201310452441A CN 103536625 B CN103536625 B CN 103536625B
- Authority
- CN
- China
- Prior art keywords
- cerium oxide
- oxide composite
- mixed solution
- beta
- preparation
- 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
Abstract
The present invention relates to a kind of nanometer cerium oxide composite and preparation method thereof, antioxidant, nanometer cerium oxide composite of the present invention is made up of the fusiform loose structure nano-cerium oxide of grafted by beta cyclodextrin, uniform particle sizes, yardstick are little, activity good, stable in water, there is very superior oxidation resistance, preparation method productive rate is high, and cost is low, and production procedure is short.
Description
Technical field:
The present invention relates to technical field of nano material, be specifically related to a kind of nanometer cerium oxide composite and preparation method thereof, antioxidant.
Technical background:
Oxidation reaction is the critical process of life continuation, but it is also one of mankind arch-criminal producing disease simultaneously.Biological cells and tissues can decompose by free radical or oxidant, affects metabolic function, and can cause different health problems.Under normal circumstances, cell can resist the injury that these free radicals bring, but due to diet unhealthy, the appearance of the problems such as Exposure to Sunlight, pressure, environmental pollution, the protection of cell self seems very limited.If too much oxyradical can be eliminated, many free radicals are caused and aging-related disease can both prevent.Such as common cancer, arteriosclerosis, diabetes, cataract, cardiovascular diseases, senile dementia, arthritis etc., these diseases are all considered to relevant to free radical.So it needs to absorb some extra antioxidants, prevent cell rapid senescence or be killed.Research proves, the antioxidant system of human body be one can comparable with immune system, have and improve and the system of sophisticated functions, body antioxidative ability is stronger, more healthy, and life is also longer.In the last few years, along with people more and more pay attention to health, the research and development of antioxidant also more and more cause interest widely.
The research of current antioxidant mainly concentrates on organic or natural product, along with nano science is flourish, inorganic nano material is also little by little applied to the fields such as biological and medical treatment, and the unique features that such as cerium oxide nanostructure coexists due to its trivalent and tetravalence is studied fast by as antioxidant.But these materials are widely applied to and medically remain a huge challenge, because inorganic matter is difficult to be dispersed in biological solutions, or can not active somatic cell be applied to some toxic components during its synthesis, therefore synthesize the nano-anti-oxidation inorganic matter that can combine with Biomedia and become particularly important.Have researcher to utilize dextran, dispersibility in a solvent and stability are improved to help it in the surface that polymer etc. are grafted on nano-cerium oxide, expand its application in antioxidation.But these method steps are more numerous and diverse, building-up process is difficult to control, and conditional request is harsh, is difficult to realize industrialization; And because later-stage utilization molecule combines, reduce the oxidation resistance of material itself to a great extent.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of nanometer cerium oxide composite and preparation method thereof, antioxidant, nanometer cerium oxide composite of the present invention is made up of the fusiform loose structure nano-cerium oxide of grafted by beta cyclodextrin, uniform particle sizes, yardstick are little, activity good, stable in water, have very superior oxidation resistance, preparation method productive rate is high, cost is low, and production procedure is short.
The technical solution used in the present invention is:
A kind of nanometer cerium oxide composite, is made up of the fusiform loose structure nano-cerium oxide of grafted by beta cyclodextrin; The length of described fusiform loose structure nano-cerium oxide is 50 ~ 90nm, wide 20 ~ 50nm.
A preparation method for nanometer cerium oxide composite, step comprises:
A, by beta-schardinger dextrin-and the water-soluble obtained mixed solution of cerous salt, in mixed solution, the ratio of the amount of substance of beta-schardinger dextrin-and cerous salt is 0.1 ~ 2:1, described beta-schardinger dextrin-concentration is 0.00125mol/L ~ 0.4mol/L, and the concentration of cerous salt is 0.0125mol/L ~ 0.2mol/L; Described cerous salt is selected from cerium chloride, one or more in cerous nitrate and cerous sulfate;
B, in the obtained mixed solution of steps A, add alkali and fully stir, making mixed solution produce cloud mixture; Described alkali is 3.75 ~ 30:1 with the ratio of the amount of substance of cerous salt; Described alkali is selected from sodium hydroxide and/or potassium hydroxide;
C, mixed liquor obtained for step B is heated to 100-200 DEG C, reaction 0.5-36 hour, is precipitated thing, is filtered and washes clean by precipitate, dry, i.e. the fusiform loose structure nano-cerium oxide of obtained grafted by beta cyclodextrin and nanometer cerium oxide composite;
A kind of antioxidant, is made up of nanometer cerium oxide composite.
Nanometer cerium oxide composite uniform particle sizes prepared by the present invention, yardstick is little, activity good, stable in water, has very superior oxidation resistance; Preparation method productive rate is high, and cost is low, and production procedure is short, and method is simply controlled, and equipment requirements is not high, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the nanometer cerium oxide composite that embodiment 1 obtains;
Fig. 2 is scanning electron microscopy (SEM) photo of the nanometer cerium oxide composite that embodiment 1 obtains;
Fig. 3 is transmission electron microscopy (TEM) photo of the nanometer cerium oxide composite that embodiment 1 obtains;
Fig. 4 is the UV transmittance test pattern of the anti-hydrogen peroxide oxidation of nanometer cerium oxide composite that embodiment 1 obtains,
In figure, a is the light transmittance curve of the mixed liquor of nanometer cerium oxide composite and water; B is the light transmittance curve immediately recorded after the mixed liquor of nanometer cerium oxide composite and water adds hydrogen peroxide; C is that the mixed liquor of nanometer cerium oxide composite and water adds the light transmittance curve recorded after hydrogen peroxide places 5 days; D is that the mixed liquor of nanometer cerium oxide composite and water adds the light transmittance curve recorded after hydrogen peroxide places 20 days;
Fig. 5 is scanning electron microscopy (SEM) photo of the nanometer cerium oxide composite that embodiment 2 obtains;
Fig. 6 is scanning electron microscopy (SEM) photo of the nanometer cerium oxide composite that embodiment 3 obtains;
Fig. 7 is scanning electron microscopy (SEM) photo of the nanometer cerium oxide composite that embodiment 4 obtains;
Fig. 8 is scanning electron microscopy (SEM) photo of the nanometer cerium oxide composite that embodiment 5 obtains.
Detailed description of the invention
Embodiment 1
A kind of nanometer cerium oxide composite, is made up of the fusiform loose structure nano-cerium oxide of grafted by beta cyclodextrin; The length of described fusiform loose structure nano-cerium oxide is 60-80nm, wide 20-30nm.
A preparation method for nanometer cerium oxide composite, step comprises:
A, by beta-schardinger dextrin-and the water-soluble obtained mixed solution of cerous nitrate, in mixed solution, the ratio of the amount of substance of beta-schardinger dextrin-and cerous nitrate is 1:1, and described beta-schardinger dextrin-concentration is 0.1mol/L, and the concentration of cerous nitrate is 0.1mol/L;
B, in the obtained mixed solution of steps A, add sodium hydroxide and fully stir; Described sodium hydroxide is 15:1 with the ratio of the amount of substance of cerous nitrate;
C, mixed liquor obtained for step B is heated to 120 DEG C, react 3 hours, be precipitated thing, cooled, filter, be washed to neutrality by precipitate, 60 DEG C of vacuum drying 12h obtain light yellow product, namely obtain nanometer cerium oxide composite.
A kind of antioxidant, is made up of nanometer cerium oxide composite.
The concentration of obtained nanometer cerium oxide composite by 10g/L be dispersed in water, left at room temperature was observed after one month, and nanometer cerium oxide composite is still dispersed in water uniformly, illustrated that the mixed liquor stability of itself and water is very good, had good water solublity.
The composite of preparation is carried out oxidation resistance test: the concentration of composite by 10g/L be dispersed in water, get the mixed liquor of 4 parts of each 3mL composites and water, test the light transmittance of a copy of it mixed liquor with ultraviolet-visible spectrophotometer; Then the hydrogen peroxide one of 30% is respectively added to all the other 3 portions of mixed liquors, the light transmittance of test a copy of it mixed liquor; Then transmittance is tested after residue 2 portions of mixed liquors being placed 5 days, 20 days respectively, test result is shown in Fig. 4, and as can be seen from Figure, nanometer cerium oxide composite has good oxidation resistance in aqueous, in figure, a and d overlaps substantially, illustrates that cyclicity is very good.
Embodiment 2
A kind of nanometer cerium oxide composite, is made up of the fusiform loose structure nano-cerium oxide of grafted by beta cyclodextrin; The length of described fusiform loose structure nano-cerium oxide is 70-80nm, wide 20-30nm.
A preparation method for nanometer cerium oxide composite, step comprises:
A, by beta-schardinger dextrin-and the water-soluble obtained mixed solution of cerium chloride, in mixed solution, the ratio of the amount of substance of beta-schardinger dextrin-and cerium chloride is 0.5:1, and described beta-schardinger dextrin-concentration is 0.1mol/L, and the concentration of cerium chloride is 0.2mol/L;
B, in the obtained mixed solution of steps A, add potassium hydroxide and fully stir, making mixed solution produce cloud mixture; Described potassium hydroxide is 5:1 with the ratio of the amount of substance of cerium chloride;
C, mixed liquor obtained for step B is heated to 180 DEG C, react 0.5 hour, be precipitated thing, precipitate is filtered and washes clean, 60 DEG C of vacuum drying 12h, namely obtain fusiform loose structure nano-cerium oxide and the nanometer cerium oxide composite of grafted by beta cyclodextrin;
A kind of antioxidant, is made up of nanometer cerium oxide composite.
Embodiment 3
A kind of nanometer cerium oxide composite, is made up of the fusiform loose structure nano-cerium oxide of grafted by beta cyclodextrin; The length of described fusiform loose structure nano-cerium oxide is 70-90nm, wide 30-50nm.
A preparation method for nanometer cerium oxide composite, step comprises:
A, by beta-schardinger dextrin-and the water-soluble obtained mixed solution of cerous nitrate, in mixed solution, the ratio of the amount of substance of beta-schardinger dextrin-and cerous nitrate is 2:1, and described beta-schardinger dextrin-concentration is 0.025mol/L, and the concentration of cerous nitrate is 0.0125mol/L;
B, in the obtained mixed solution of steps A, add sodium hydroxide and fully stir, making mixed solution produce cloud mixture; Described sodium hydroxide is 3.75:1 with the ratio of the amount of substance of cerous nitrate;
C, mixed liquor obtained for step B is heated to 150 DEG C, react 20 hours, be precipitated thing, precipitate is filtered and washes clean, 60 DEG C of vacuum drying 12h, namely obtain fusiform loose structure nano-cerium oxide and the nanometer cerium oxide composite of grafted by beta cyclodextrin;
A kind of antioxidant, is made up of nanometer cerium oxide composite.
Embodiment 4
A kind of nanometer cerium oxide composite, is made up of the fusiform loose structure nano-cerium oxide of grafted by beta cyclodextrin; The length of described fusiform loose structure nano-cerium oxide is 60-90nm, wide 20-30nm.
A preparation method for nanometer cerium oxide composite, step comprises:
A, by beta-schardinger dextrin-and the water-soluble obtained mixed solution of cerous sulfate, in mixed solution, the ratio of the amount of substance of beta-schardinger dextrin-and cerous sulfate is 0.1:1, and described beta-schardinger dextrin-concentration is 0.002mol/L, and the concentration of cerous sulfate is 0.02mol/L;
B, in the obtained mixed solution of steps A, add sodium hydroxide and fully stir, making mixed solution produce cloud mixture; Described sodium hydroxide is 30:1 with the ratio of the amount of substance of cerous sulfate;
C, mixed liquor obtained for step B is heated to 100 DEG C, react 36 hours, be precipitated thing, precipitate is filtered and washes clean, 60 DEG C of vacuum drying 12h, namely obtain fusiform loose structure nano-cerium oxide and the nanometer cerium oxide composite of grafted by beta cyclodextrin;
A kind of antioxidant, is made up of nanometer cerium oxide composite.
Embodiment 5
A kind of nanometer cerium oxide composite, is made up of the fusiform loose structure nano-cerium oxide of grafted by beta cyclodextrin; The length of described fusiform loose structure nano-cerium oxide is 60-80nm, wide 30-50nm.
A preparation method for nanometer cerium oxide composite, step comprises:
A, by beta-schardinger dextrin-and the water-soluble obtained mixed solution of cerous nitrate, in mixed solution, the ratio of the amount of substance of beta-schardinger dextrin-and cerous nitrate is 2:1, and described beta-schardinger dextrin-concentration is 0.4mol/L, and the concentration of cerous nitrate is 0.2mol/L;
B, in the obtained mixed solution of steps A, add sodium hydroxide and fully stir, making mixed solution produce cloud mixture; Described sodium hydroxide is 10:1 with the ratio of the amount of substance of cerous nitrate;
C, mixed liquor obtained for step B is heated to 200 DEG C, react 12 hours, be precipitated thing, precipitate is filtered and washes clean, 60 DEG C of vacuum drying 12h, namely obtain fusiform loose structure nano-cerium oxide and the nanometer cerium oxide composite of grafted by beta cyclodextrin;
A kind of antioxidant, is made up of nanometer cerium oxide composite.
Claims (6)
1. a nanometer cerium oxide composite, is made up of the fusiform loose structure nano-cerium oxide of grafted by beta cyclodextrin; The length of described fusiform loose structure nano-cerium oxide is 50 ~ 90nm, wide 20 ~ 50nm;
The preparation method step of described nanometer cerium oxide composite comprises:
A, by beta-schardinger dextrin-and the water-soluble obtained mixed solution of cerous salt, in mixed solution, the ratio of the amount of substance of beta-schardinger dextrin-and cerous salt is 0.1 ~ 2:1;
B, in the obtained mixed solution of steps A, add alkali and fully stir, making mixed solution produce cloud mixture;
C, mixed liquor obtained for step B is heated to 100-200 DEG C, reaction 0.5-36 hour, is precipitated thing, is filtered and washes clean by precipitate, dry, i.e. the fusiform loose structure nano-cerium oxide of obtained grafted by beta cyclodextrin and nanometer cerium oxide composite.
2. a preparation method for nanometer cerium oxide composite, step comprises:
A, by beta-schardinger dextrin-and the water-soluble obtained mixed solution of cerous salt, in mixed solution, the ratio of the amount of substance of beta-schardinger dextrin-and cerous salt is 0.1 ~ 2:1;
B, in the obtained mixed solution of steps A, add alkali and fully stir, making mixed solution produce cloud mixture;
C, mixed liquor obtained for step B is heated to 100-200 DEG C, reaction 0.5-36 hour, is precipitated thing, is filtered and washes clean by precipitate, dry, i.e. the fusiform loose structure nano-cerium oxide of obtained grafted by beta cyclodextrin and nanometer cerium oxide composite.
3. preparation method as claimed in claim 2, in described steps A, beta-schardinger dextrin-concentration is 0.00125mol/L ~ 0.4mol/L, and the concentration of cerous salt is 0.0125mol/L ~ 0.2mol/L.
4. preparation method as claimed in claim 2, in described steps A, cerous salt is selected from cerium chloride, one or more in cerous nitrate and cerous sulfate.
5. preparation method as claimed in claim 2, in described step B, alkali is 3.75 ~ 30:1 with the ratio of the amount of substance of cerous salt.
6. preparation method as claimed in claim 2, in described step B alkali be selected from sodium hydroxide and
/or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310452441.0A CN103536625B (en) | 2013-09-27 | 2013-09-27 | A kind of nanometer cerium oxide composite and preparation method thereof, antioxidant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310452441.0A CN103536625B (en) | 2013-09-27 | 2013-09-27 | A kind of nanometer cerium oxide composite and preparation method thereof, antioxidant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103536625A CN103536625A (en) | 2014-01-29 |
| CN103536625B true CN103536625B (en) | 2016-01-06 |
Family
ID=49960739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310452441.0A Expired - Fee Related CN103536625B (en) | 2013-09-27 | 2013-09-27 | A kind of nanometer cerium oxide composite and preparation method thereof, antioxidant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103536625B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106975100B (en) * | 2016-01-15 | 2019-06-11 | 浙江大学 | A kind of nanocomposite and its preparation method and application of cerium oxide/mesoporous silicon |
| CN106860427B (en) * | 2017-01-19 | 2019-12-17 | 浙江大学 | Cerium oxide/iron oxide/mesoporous silicon nano composite material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762579A (en) * | 2005-09-09 | 2006-04-26 | 清华大学 | Method for preparing large pore capacity, high specific surface area alumina |
| CN1840480A (en) * | 2005-03-29 | 2006-10-04 | 中国科学院大连化学物理研究所 | Cerium oxide nano materials and its preparation and use |
| CN101407330A (en) * | 2008-10-30 | 2009-04-15 | 上海大学 | Method of preparing cerium oxide nano-rod |
| CN101549881A (en) * | 2009-05-14 | 2009-10-07 | 浙江大学 | Walnut shaped hydroxyl cerous carbonate and cerium oxide nanostructure, and preparation method thereof |
| CN102285678A (en) * | 2011-06-09 | 2011-12-21 | 北京大学 | Method for preparing cerium oxide nano particles and antioxidation use thereof |
| CN103101955A (en) * | 2012-11-20 | 2013-05-15 | 陕西科技大学 | Method for preparing CeO2 nanometer solid sphere by using CTAB (Cetyltrimethyl Ammonium Bromide) as soft template |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9550162B2 (en) * | 2005-09-19 | 2017-01-24 | Intematix Corporation | Printing liquid solution arrays for inorganic combinatorial libraries |
-
2013
- 2013-09-27 CN CN201310452441.0A patent/CN103536625B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840480A (en) * | 2005-03-29 | 2006-10-04 | 中国科学院大连化学物理研究所 | Cerium oxide nano materials and its preparation and use |
| CN1762579A (en) * | 2005-09-09 | 2006-04-26 | 清华大学 | Method for preparing large pore capacity, high specific surface area alumina |
| CN101407330A (en) * | 2008-10-30 | 2009-04-15 | 上海大学 | Method of preparing cerium oxide nano-rod |
| CN101549881A (en) * | 2009-05-14 | 2009-10-07 | 浙江大学 | Walnut shaped hydroxyl cerous carbonate and cerium oxide nanostructure, and preparation method thereof |
| CN102285678A (en) * | 2011-06-09 | 2011-12-21 | 北京大学 | Method for preparing cerium oxide nano particles and antioxidation use thereof |
| CN103101955A (en) * | 2012-11-20 | 2013-05-15 | 陕西科技大学 | Method for preparing CeO2 nanometer solid sphere by using CTAB (Cetyltrimethyl Ammonium Bromide) as soft template |
Non-Patent Citations (3)
| Title |
|---|
| Preparation and Characterization of CeO2 with Different Particle Sizes and Morphology;Lai Jun Wang et al.;《Solid State Phenomena》;20071231;第121-123卷;第21-24页，尤其第21页最后1段 * |
| 以环糊精为模板剂制备不同粒径CeO2 纳米粒子;王来军等;《分子催化》;20060430;第20卷(第2期);第179页第1.1节、右栏最后1段，第180页第右栏第2.1节 * |
| 贵金属/氧化铈低维纳米结构的制备及其CO催化氧化性能研究;牛付欢;《万方数据企业知识服务平台》;20101222;正文第2页第4段，第17页第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103536625A (en) | 2014-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Prominent dual Z-scheme mechanism on phase junction WO3/CdS for enhanced visible-light-responsive photocatalytic performance on imidacloprid degradation | |
| Ji et al. | 2D-2D stacking of graphene-like g-C3N4/Ultrathin Bi4O5Br2 with matched energy band structure towards antibiotic removal | |
| Wu et al. | Core-shell structured Cu2O@ HKUST-1 heterojunction photocatalyst with robust stability for highly efficient tetracycline hydrochloride degradation under visible light | |
| Qian et al. | Facile preparation and highly efficient photodegradation performances of self-assembled Artemia eggshell-ZnO nanocomposites for wastewater treatment | |
| Huang et al. | Synthesis of magnetic CoFe2O4/g-C3N4 composite and its enhancement of photocatalytic ability under visible-light | |
| Ma et al. | In-situ prepared MIL-53 (Fe)/BiOI photocatalyst for efficient degradation of tetracycline under visible-light driven photo-Fenton system: Investigation of performance and mechanism | |
| Zhang et al. | Metal organic frameworks constructed heterojunction with α-NiS-β-NiS/CdS: The effect of organic-ligand in UiO-66 for charge transfer of photocatalytic hydrogen evolution | |
| Cao et al. | Low temperature synthesis of novel rodlike Bi5O7I with visible light photocatalytic performance | |
| Gu et al. | Morphology modulation of hollow-shell ZnSn (OH) 6 for enhanced photodegradation of methylene blue | |
| Cai et al. | Hierarchical ZnO/S, N: GQD composites: biotemplated synthesis and enhanced visible-light-driven photocatalytic activity | |
| Zhu et al. | S-scheme photocatalysis induced by ultrathin TiO2 (B) nanosheets-anchored hierarchical In2S3 spheres for boosted photocatalytic activity | |
| Ao et al. | A novel heterostructured plasmonic photocatalyst with high photocatalytic activity: Ag@ AgCl nanoparticles modified titanium phosphate nanoplates | |
| Liu et al. | Simple synthesis of BiOAc/BiOBr heterojunction composites for the efficient photocatalytic removal of organic pollutants | |
| Mu et al. | 2D/3D S-scheme heterojunction of carbon nitride/iodine-deficient bismuth oxyiodide for photocatalytic hydrogen production and bisphenol A degradation | |
| CN102275986A (en) | Controllable hydro-thermal preparation method for titanium dioxide nanobelts of different crystal forms | |
| Li et al. | Magnetically recoverable Cu2O/Fe3O4 composite photocatalysts: Fabrication and photocatalytic activity | |
| CN103055903B (en) | Preparation method of visible light catalytic material with adjustable BiOI-AgI spherical solid solution | |
| Arshadnia et al. | SnFe2O4/SnO2/PANI magnetically separable photocatalyst for decolorization of two dye mixture in aqueous solution | |
| CN102211200B (en) | Method for synthesizing eggplant-shaped Ag-Ag2S nano heterojunction in one-step | |
| CN104150541B (en) | A kind of grain of rice shape α-Fe 2o 3the preparation method of nanometer powder | |
| Zhang et al. | Synthesis of CaIn2S4/TiO2 heterostructures for enhanced UV–visible light photocatalytic activity | |
| CN103157495A (en) | Au/BiOBr0.2I0.8 visible-light-induced catalyst and preparation method thereof | |
| CN106693994A (en) | Preparation and application of core-shell structure bismuth sulfide@copper sulfide composite microspheres | |
| Zhang et al. | Shape-dependent synthesis and photocatalytic degradation by Cu2O nanocrystals: Kinetics and photocatalytic mechanism | |
| Dharmaraja et al. | Investigation on photocatalytic activity of ZnS/NiFe2O4 NCs under sunlight irradiation via a novel two-step synthesis approach |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211012 Address after: 150010 building 2a, Yingbin Road concentration area, GaoKai District, Harbin City, Heilongjiang Province Patentee after: Harbin Bense Biotechnology Co.,Ltd. Address before: 241000 Wuhu Road, Yijiang District, Anhui, Patentee before: ANHUI NORMAL University |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160106 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |