CN106219606B - A kind of nanometer of flower ball-shaped Ag3VO4Preparation method - Google Patents
A kind of nanometer of flower ball-shaped Ag3VO4Preparation method Download PDFInfo
- Publication number
- CN106219606B CN106219606B CN201610547784.9A CN201610547784A CN106219606B CN 106219606 B CN106219606 B CN 106219606B CN 201610547784 A CN201610547784 A CN 201610547784A CN 106219606 B CN106219606 B CN 106219606B
- Authority
- CN
- China
- Prior art keywords
- solution
- shaped
- nanometer
- mixed solution
- flower ball
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
A kind of nanometer of flower ball-shaped Ag3VO4Preparation method, using precipitation assisting alcohol-hydrothermal method synthesis, preparation method includes：Silver nitrate is added to polyvinylpyrrolidone and the ammonium metavanadate (NH of a concentration of 0.1~0.3mol/L4VO3) in mixed solution, adjust pH value to after 4~12 with the NaOH solution of 0.2mol/L, 4~12h is heat-treated at 80~180 DEG C.It is washed respectively with distilled water and absolute ethyl alcohol after obtained sediment filtering, and dry in 60~80 DEG C of vacuum drying chamber.Obtained vanadic acid silver powder is mono-crystalline structures, and chemical composition is uniform, and purity is higher, has larger specific surface area, improves the photocatalysis performance of material.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, are related to semiconductor nano material and prepare and apply, and in particular to Yi Zhongna
The spherical Ag of popped rice3VO4Preparation method.
Background technology
Photocatalysis technology is the emerging technology of a field of energy environment, such as TiO2For the catalysis material of representative, because
Can the organic pollution exhaustive oxidation in environment be decomposed into H at room temperature2O、CO2Etc. nontoxic object, and with it is efficient,
The advantages that at low cost, catalyst chemically-resistant and photochemical corrosion and more and more paid close attention to by people.Vanadate is because with good
Good photocatalysis performance and be widely studied, such as BiVO4、InVO4、FeVO4Materials is waited to be widely used in photocatalysis field, vanadium
Sour lithium material also has remarkable progress in field of batteries.
Ag3VO4Higher energy conduction band formed by the 3d orbital hybridizations of the 5s and V of Ag, and its low energy valence band by Ag 4d tracks and
The 2p orbital hybridizations of O form.The valence band structure of hydridization so that energy level is more active, leads to its monoclinic phase band gap width ＜ 2.7
eV.The design feature causes silver vanadate to have wider response range to visible ray, has potential application in photocatalysis field
Prospect.
At present, the pattern of silver vanadate prepared by the methods of hydro-thermal method, microwave-hydrothermal method proposed both at home and abroad includes：Particle
Shape, square, threadiness etc..Chinese invention issued patents the 201310257173.7th disclose a kind of silver vanadate nanofiber
Photochemical catalyst uses method of electrostatic spinning to prepare, but requires height to moisture etc., and technical difficulty is big.No. 201210531539.0
A kind of rodlike silver vanadate nano-photocatalyst is disclosed, rodlike vanadic acid silver micro-crystallite, but technical difficulty are prepared using double note precipitation method
Greatly, and to prepared product preservation condition it requires high.No. 201310287983.7 discloses a kind of vanadic acid nano silver wire
Preparation method, but reaction time is long.CTAB-assisted hydrothermal synthesis of silver
Vanadates and their photocatalytic characterization.Chao-Ming Huang et al. use
Ag is prepared as the hydro-thermal combination heat treatment mode of surfactant in CTAB3VO4With Ag4V2O7Mixed phase, product is pure
Degree is not high, and size is larger.The preparation method of the silver vanadate of special appearance is also seldom at present, therefore to the silver vanadate of special appearance
Research be of great significance.
Invention content
The present invention in view of the above shortcomings of the prior art, proposes a kind of nanometer of flower ball-shaped Ag3VO4Preparation method, this method
Reaction condition is mild, easy to operate, repeatedly can largely repeat to prepare, and prepare silver vanadate product purity height, property is stablized.
To achieve these goals, the present invention uses following technical scheme.
A kind of nanometer of flower ball-shaped Ag3VO4Preparation method, include the following steps：
(1) polyvinylpyrrolidone is added in ammonium metavanadate aqueous solution, stirred evenly, obtain mixed solution A；
(2) silver nitrate solution is added drop-wise in mixed solution A, stirs lower 1~3h, obtain mixed solution B；
(3) mixed solution pH value is adjusted to after 4~12, after carrying out 4~12h of hydro-thermal reaction at 80~180 DEG C, will be reacted
Precipitation is obtained by filtration in liquid, and precipitation is washed, dry, obtains a nanometer flower ball-shaped Ag3VO4。
The present invention, which further improves, to be, a concentration of 0.1~0.3mol/L of ammonium metavanadate aqueous solution in step (1),
The amount ratio of polyvinylpyrrolidone and ammonium metavanadate aqueous solution is (0.01~0.04) g：(20~60) mL.
Further improve of the invention is, stirs in step (1) and is carried out at 40~100 DEG C, and stir
Time is 1~3h.
The present invention, which further improves, to be, a concentration of 0.1~0.3mol/L of the silver nitrate solution described in step (2),
The amount ratio of silver nitrate solution and ammonium metavanadate aqueous solution is (20~60) mL：(10~60) mL.
Further improve of the invention is that step (3) adjusts mixed solution using the NaOH solution of 0.1~0.3mol/L
The pH value of B.
Further improve of the invention is, adjusts mixed solution pH value to 1~8h of stirring after 4~12, then carry out hydro-thermal
Reaction.
Further improve of the invention is that the hydro-thermal reaction described in step (3) is carried out in autoclave.
Further improve of the invention is that the washing described in step (3) is to wash precipitation with distilled water and ethyl alcohol.
Further improve of the invention is that the drying described in step (3) is carried out at 40~80 DEG C.
Compared with prior art, the present invention can obtain following advantageous effect：
(1) precipitation auxiliary hydrothermal method of the present invention is with NH4VO3As vanadium source, with AgNO3As silver-colored source, PVP
As surfactant, the pH value of solution is adjusted with NaOH aqueous solutions, then hydro-thermal reaction is carried out at 80~150 DEG C, light is made
The silver vanadate of the flower ball-shaped of the good size uniformity of catalytic performance.
(2) present invention synthesizes silver vanadate with wet chemistry method, realizes the mixing of Ag, V, O on a molecular scale.Product size
Uniformly, and it is mono-crystalline structures.
(3) precipitation auxiliary water-heat process of the present invention, flow is short, simple for process, and product quality is stable and pattern is equal
One, it is easy to accomplish industrialization.
Description of the drawings
Fig. 1 is the X ray diffracting spectrum of silver vanadate that the present invention is prepared under the conditions of embodiment 3.
Fig. 2 is the scanning electron microscope diagram of silver vanadate that the present invention is prepared under the conditions of embodiment 3, wherein, figure (a) is
The scanning figure of PVP prepared catalysts is not added with, figure (b) is scanning figures of the PVP as surfactant prepared catalyst.
Fig. 3 is the silver vanadate that the present invention is prepared under the conditions of embodiment 3 under visible light illumination to the degradation of rhodamine B
Curve graph.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described in further detail the present invention：
Embodiment 1
(1) 0.01g polyvinylpyrrolidones (PVP) are added to the ammonium metavanadate (NH of 20mL 0.1mol/L4VO3) water-soluble
In liquid, magnetic agitation 1h, is cooled to room temperature at 90 DEG C, obtains mixed solution A.
(2) by the silver nitrate (AgNO of 60mL 0.3mol/L3) solution is added drop-wise in mixed solution A, magnetic agitation 1h is obtained
To mixed solution B.
(3) using the pH value of the NaOH solution of 0.1mol/L adjusting mixed solution B to magnetic agitation 3h after 12, at 180 DEG C
Reaction solution after reaction, is obtained by filtration precipitation, distilled water is used respectively after obtained sediment filtering by lower hydro-thermal reaction 4h
It is and dry in 70 DEG C of baking oven with ethyl alcohol centrifuge washing, obtain a nanometer flower ball-shaped Ag3VO4。
Embodiment 2
(1) 0.02g polyvinylpyrrolidones (PVP) are added to the ammonium metavanadate (NH of 20mL 0.1mol/L4VO3) water-soluble
In liquid, magnetic agitation 1h, is cooled to room temperature at 80 DEG C, obtains mixed solution A.
(2) by the silver nitrate (AgNO of 60mL 0.3mol/L3) solution is added drop-wise in mixed solution A, magnetic agitation 1h is obtained
To mixed solution B.
(3) using the pH value of the NaOH solution of 0.2mol/L adjusting mixed solution B to magnetic agitation 3h after 10, at 150 DEG C
Reaction solution after reaction, is obtained by filtration precipitation, distilled water is used respectively after obtained sediment filtering by lower hydro-thermal reaction 6h
It is and dry in 70 DEG C of baking oven with ethyl alcohol centrifuge washing, obtain a nanometer flower ball-shaped Ag3VO4。
Embodiment 3
(1) 0.03g polyvinylpyrrolidones (PVP) are added to the ammonium metavanadate (NH of 20mL 0.1mol/L4VO3) water-soluble
In liquid, magnetic agitation 1h, is cooled to room temperature at 60 DEG C, obtains mixed solution A.
(2) by the silver nitrate (AgNO of 60mL 0.3mol/L3) solution is added drop-wise in mixed solution A, magnetic agitation 1h is obtained
To mixed solution B.
(3) using the pH value of the NaOH solution of 0.3mol/L adjusting mixed solution B to magnetic agitation 3h after 7, at 120 DEG C
Hydro-thermal reaction 8h after reaction, is centrifuged with distilled water and ethyl alcohol respectively after reaction solution is filtered obtained sediment filtering
Washing, and it is dry in 70 DEG C of baking oven, obtain a nanometer flower ball-shaped Ag3VO4。
Referring to Fig. 1, by XRD diffracting spectrums, it is clear that Ag prepared by the present invention3VO4For pure phase monocrystalline knot
Structure；
Referring to Fig. 2, from the stereoscan photograph of Fig. 2 (a) and Fig. 2 (b) can be seen that the lamellar spacing 10nm of flower ball-shaped~
20nm is self-assembled into flower ball-shaped, a diameter of 2~5 μm of bouquet；
Referring to Fig. 3, by 0.05g, the powder is put into 50mL rhodamine Bs solution (rhodamine B concentration 10mg/L), visible
Under the conditions of light irradiation, the degradation rate of rhodamine B is up to more than 80% after reaction 4h.
Embodiment 4
(1) 0.04g polyvinylpyrrolidones (PVP) are added to the ammonium metavanadate (NH of 20mL 0.1mol/L4VO3) water-soluble
In liquid, magnetic agitation 1h, is cooled to room temperature at 40 DEG C, obtains mixed solution A.
(2) by the silver nitrate (AgNO of 60mL 0.3mol/L3) solution is added drop-wise in mixed solution A, magnetic agitation 1h is obtained
To mixed solution B.
(3) using the pH value of the NaOH solution of 0.2mol/L adjusting mixed solution B to magnetic agitation 3h after 4, at 100 DEG C
Reaction solution after reaction, is obtained by filtration precipitation, distilled water is used respectively after obtained sediment filtering by hydro-thermal reaction 10h
It is and dry in 70 DEG C of baking oven with ethyl alcohol centrifuge washing, obtain a nanometer flower ball-shaped Ag3VO4。
Embodiment 5
(1) polyvinylpyrrolidone is added in ammonium metavanadate aqueous solution, stirs 3h at 40 DEG C, obtain mixed solution
A；Wherein, the amount ratio of a concentration of 0.2mol/L of ammonium metavanadate aqueous solution, polyvinylpyrrolidone and ammonium metavanadate aqueous solution
For 0.02g：40mL.
(2) silver nitrate solution is added drop-wise in mixed solution A, stirs lower 2h, obtain mixed solution B；Wherein, silver nitrate is molten
The amount ratio of a concentration of 0.1mol/L of liquid, silver nitrate solution and ammonium metavanadate aqueous solution is 20mL：40mL.
(3) using 1h is stirred after the NaOH solution of 0.1mol/L adjusting mixed solution pH value to 8, then in height at 80 DEG C
It presses after carrying out hydro-thermal reaction 12h in reaction kettle, precipitation is obtained by filtration in reaction solution, precipitate through distilled water and ethyl alcohol washing, 40
It is dry at DEG C, obtain a nanometer flower ball-shaped Ag3VO4。
Embodiment 6
(1) polyvinylpyrrolidone is added in ammonium metavanadate aqueous solution, 1h is stirred at 100 DEG C, obtain mixing molten
Liquid A；Wherein, the dosage of a concentration of 0.3mol/L of ammonium metavanadate aqueous solution, polyvinylpyrrolidone and ammonium metavanadate aqueous solution
Than for 0.04g：60mL.
(2) silver nitrate solution is added drop-wise in mixed solution A, stirs lower 3h, obtain mixed solution B；Wherein, silver nitrate is molten
The amount ratio of a concentration of 0.2mol/L of liquid, silver nitrate solution and ammonium metavanadate aqueous solution is 40mL：60mL.
(3) mixed solution pH value is adjusted to 8h is stirred after 5 using the NaOH solution of 0.3mol/L, then at 140 DEG C
After carrying out hydro-thermal reaction 7h in autoclave, precipitation is obtained by filtration in reaction solution, precipitate washed through distilled water and ethyl alcohol,
It is dry at 80 DEG C, obtain a nanometer flower ball-shaped Ag3VO4。
Flower ball-shaped vanadic acid silver nano material photochemical catalyst produced by the present invention, monocline crystalline phase, the composition expression formula of the particle
For Ag3VO4.Nanoscale twins thickness 10nm~20nm is self-assembled into flower ball-shaped, a diameter of 2~5 μm of bouquet.
The silver vanadate is the pure phase silver vanadate obtained under condition of different pH.The vanadic acid silver nano material of flower ball-shaped is using heavy
The hydro-thermal method synthesis for auxiliary of forming sediment.Chemical composition is uniform, and purity is higher, has larger specific surface area, and the light for improving material is urged
Change performance.
Claims (5)
1. a kind of nanometer of flower ball-shaped Ag3VO4Preparation method, which is characterized in that include the following steps：
(1) polyvinylpyrrolidone is added in ammonium metavanadate aqueous solution, stirred evenly, obtain mixed solution A；
(2) silver nitrate solution is added drop-wise in mixed solution A, stirs lower 1~3h, obtain mixed solution B；
(3) mixed solution B pH value is adjusted to after 4~12, stirs 1~8h, 4~12h of hydro-thermal reaction is carried out at 80~180 DEG C
Afterwards, precipitation is obtained by filtration in reaction solution, precipitation is washed, dry, obtains a nanometer flower ball-shaped Ag3VO4；
A concentration of 0.1~0.3mol/L of ammonium metavanadate aqueous solution in step (1)；
Stirring carries out at 40~100 DEG C in step (1), and the time stirred is 1~3h；
The amount ratio of polyvinylpyrrolidone and ammonium metavanadate aqueous solution is (0.01~0.04) g：(20~60) mL；
A concentration of 0.1~0.3mol/L of silver nitrate solution described in step (2), silver nitrate solution and ammonium metavanadate aqueous solution
Amount ratio is (20~60) mL：(10~60) mL.
2. a kind of nanometer of flower ball-shaped Ag according to claim 13VO4Preparation method, which is characterized in that step (3) use
The NaOH solution of 0.1~0.3mol/L adjusts the pH value of mixed solution B.
3. a kind of nanometer of flower ball-shaped Ag according to claim 13VO4Preparation method, which is characterized in that step (3) is described
Hydro-thermal reaction be to be carried out in autoclave.
4. a kind of nanometer of flower ball-shaped Ag according to claim 13VO4Preparation method, which is characterized in that step (3) is described
Washing be to wash precipitation with distilled water and ethyl alcohol.
5. a kind of nanometer of flower ball-shaped Ag according to claim 13VO4Preparation method, which is characterized in that step (3) is described
Drying be to be carried out at 40~80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610547784.9A CN106219606B (en) | 2016-07-12 | 2016-07-12 | A kind of nanometer of flower ball-shaped Ag3VO4Preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610547784.9A CN106219606B (en) | 2016-07-12 | 2016-07-12 | A kind of nanometer of flower ball-shaped Ag3VO4Preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106219606A CN106219606A (en) | 2016-12-14 |
| CN106219606B true CN106219606B (en) | 2018-07-10 |
Family
ID=57520208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610547784.9A Active CN106219606B (en) | 2016-07-12 | 2016-07-12 | A kind of nanometer of flower ball-shaped Ag3VO4Preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106219606B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107827153B (en) * | 2017-10-31 | 2019-12-03 | 成都先进金属材料产业技术研究院有限公司 | A kind of preparation method of nanometer of silver vanadate |
| CN110759381B (en) * | 2019-11-05 | 2021-11-19 | 北华航天工业学院 | Preparation method of coral-shaped lithium vanadate nano material |
| CN115779929B (en) * | 2022-09-29 | 2024-02-23 | 南京师范大学 | Modified ZnIn 2 S 4 Photocatalyst, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354746A (en) * | 2011-11-11 | 2012-02-15 | 中南大学 | Preparation method for silver vanadate cathode material |
| CN103285861A (en) * | 2013-06-24 | 2013-09-11 | 大连民族学院 | An Ag3VO4/TiO2 compound nano-wire having visible light activity, a preparation method and applications thereof |
| CN105217683A (en) * | 2015-10-14 | 2016-01-06 | 中国科学院海洋研究所 | A kind of silver vanadate is as the application of analogue enztme |
-
2016
- 2016-07-12 CN CN201610547784.9A patent/CN106219606B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354746A (en) * | 2011-11-11 | 2012-02-15 | 中南大学 | Preparation method for silver vanadate cathode material |
| CN103285861A (en) * | 2013-06-24 | 2013-09-11 | 大连民族学院 | An Ag3VO4/TiO2 compound nano-wire having visible light activity, a preparation method and applications thereof |
| CN105217683A (en) * | 2015-10-14 | 2016-01-06 | 中国科学院海洋研究所 | A kind of silver vanadate is as the application of analogue enztme |
Non-Patent Citations (2)
| Title |
|---|
| Crystalline phases and photocatalytic activities of hydrothermal synthesis Ag3VO4 and Ag4V2O7 under visible light irradiation;Chao-Ming Huang et al.;《Applied Catalysis A: General》;20090221;第358卷;164-172 * |
| 钒酸银材料的制备及应用进展;郭志民 等;《陶瓷学报》;20140430;第35卷(第2期);139-143 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106219606A (en) | 2016-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101508464B (en) | Process for preparing anatase type nano-titanium dioxide | |
| CN101318702B (en) | Tungstic trioxide nano-slice and preparation method thereof | |
| CN104801328B (en) | Method for preparing TiO2/g-C3N4 composite photocatalyst at low temperature | |
| CN105600828B (en) | A kind of porous nano CuFe2O4Preparation method | |
| Sun et al. | Facile synthesis of BiFeO3 nanoparticles by modified microwave-assisted hydrothermal method as visible light driven photocatalysts | |
| CN105521789B (en) | A kind of porous nano BiFeO3Preparation method | |
| CN105664950B (en) | A kind of porous nano ZnFe2O4Preparation method | |
| CN106219606B (en) | A kind of nanometer of flower ball-shaped Ag3VO4Preparation method | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| Bi et al. | Constructing anatase TiO2/Amorphous Nb2O5 heterostructures to enhance photocatalytic degradation of acetaminophen and nitrogen oxide | |
| CN103691433A (en) | Ag-doped TiO2 material, and preparation method and application thereof | |
| CN105312051A (en) | Nano gold-mesoporous silica composite nanotube, preparation and applications thereof | |
| CN106881126A (en) | A kind of bismuth tungstate/bismuth phosphate heterojunction photocatalyst and its preparation method and application | |
| CN105854870B (en) | A kind of Bi2WO6Stepped recess micron ball photocatalyst and preparation method thereof | |
| Kachbouri et al. | the effect of surfactant chain length and type on the photocatalytic activity of mesoporous TiO2 nanoparticles obtained via modified sol-gel process | |
| CN102432064B (en) | Method for synthesizing nanometer titanium dioxide by reverse microemulsion carbon adsorption titanium tetrachloride hydrolytic system | |
| CN107215896A (en) | The regulation and control method of monoclinic phase pucherite appearance structure transformation | |
| CN108940315B (en) | Bismuth vanadate powder for sterilizing nano array and preparation and application thereof | |
| CN109999774B (en) | Preparation method of nano titanium dioxide/gamma-alumina composite material powder | |
| CN106179343B (en) | A kind of rapid synthesis square Ag4V2O7The method of photochemical catalyst | |
| CN108380194B (en) | Photocatalyst and preparation method and application thereof | |
| CN113070057B (en) | Photoelectric-piezoelectric composite material and preparation method thereof | |
| CN106140159B (en) | One kind quickly preparing rodlike AgVO3The method of nano-photocatalyst | |
| CN105597726A (en) | Composite photocatalyst hydrosol | |
| CN105618049B (en) | A kind of doping preparation method in situ of visible light-responsible titanium dioxide |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |