CN113998733B - TiO with continuous two-dimensional nano sheet structure 2 Method for producing materials - Google Patents
TiO with continuous two-dimensional nano sheet structure 2 Method for producing materials Download PDFInfo
- Publication number
- CN113998733B CN113998733B CN202111263396.5A CN202111263396A CN113998733B CN 113998733 B CN113998733 B CN 113998733B CN 202111263396 A CN202111263396 A CN 202111263396A CN 113998733 B CN113998733 B CN 113998733B
- Authority
- CN
- China
- Prior art keywords
- tio
- continuous
- sheet structure
- dimensional nano
- dimensional
- 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
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000002135 nanosheet Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000004729 solvothermal method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000004005 microsphere Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a TiO with a continuous two-dimensional nano-sheet structure 2 A method of preparing a material comprising: uniformly mixing a titanium source and an organic solvent, and performing solvothermal reaction for 12-24 hours at 180-220 ℃ to obtain the TiO with a special hollow structure 2 A microsphere; the organic solvent is prepared from acetic acid and acetonitrile according to a volume ratio of 1: (1-4). The invention also discloses TiO with a continuous two-dimensional nano-sheet structure 2 A material. The invention prepares the TiO with continuous two-dimensional nano-sheet structure by a simple solvothermal method 2 The material has the advantages of mild reaction condition, simple process, strong controllability and good reproducibility, and the prepared TiO 2 The material has wide application in the fields of solar cells, ion batteries, photocatalysis and the like.
Description
Technical Field
The invention relates to the technical field of inorganic nano material preparation, in particular to a preparation method of a TiO2 material with a continuous two-dimensional nano sheet structure.
Background
In recent years, with the rise of graphene materials, two-dimensional nanomaterials have attracted a great deal of research interest to a vast number of scholars. The two-dimensional material has larger transverse dimension and atomic-level thickness, and can show the characteristics of high surface atomic ratio, anisotropic electrical property, adjustable band gap, high surface reactivity and the like. Compared with the bulk material, the coordination number, bond angle and bond length of atoms on the surface of the two-dimensional material are different, and can provide abundant surface active sites for chemical reaction. And secondly, the specific surface area of the two-dimensional material is large, and in the reaction process, the two-dimensional material has larger contact area with the reaction solution, so that more reactants can be adsorbed, and the reaction can be promoted to be carried out more quickly. Again, the reduced thickness significantly reduces the distance that photo-generated charge migrates from the interior of the material to the surface of the material, thereby achieving a faster reaction kinetics process. Finally, the defect of abundant surfaces of the two-dimensional material is utilized to perform functional modification, thereby improving the light absorption capacity of the material, improving the charge separation and transfer efficiency and accelerating the surface oxidation-reduction reaction rate. Due to their unique electrical, optical, chemical properties, two-dimensional materials are widely used in the fields of optoelectronic devices, catalysis, energy storage, conversion, and the like.
TiO 2 Has the advantages of wide forbidden bandwidth, no toxicity, good chemical stability and the like, and is widely applied to the fields of solar cells, ion batteries, photocatalysis, antibacterial materials and the like in recent years. Therefore, to further improve TiO 2 The performance of the material is reasonably designed with TiO 2 Micro-nano structure for preparing TiO with two-dimensional nano structure 2 The material and the preparation method thereof are simplified, and the material has important significance.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention provides a TiO with a continuous two-dimensional nano-sheet structure 2 A preparation method of the material.
The invention provides a TiO with a continuous two-dimensional nano-sheet structure 2 A method of preparing a material comprising: uniformly mixing a titanium source and an organic solvent, and performing solvothermal reaction for 12-24 hours at 180-220 ℃ to obtain the TiO with a special hollow structure 2 A microsphere; the organic solvent is prepared from acetic acid and acetonitrile according to a volume ratio of 1: (1-4).
Preferably, the titanium source is tetra-n-butyl titanate, tetra-isopropyl titanate, or a combination thereof.
Preferably, the volume ratio of the titanium source to the organic solvent is 1: (20-30).
TiO with continuous two-dimensional nano sheet structure 2 The material is prepared by the preparation method.
Preferably, the TiO 2 The material is formed by continuous two-dimensional TiO 2 Nanoplatelets of the two-dimensional TiO 2 The thickness of the nano-sheet is 10-15nm.
The beneficial effects of the invention are as follows:
the invention adopts the mixture of two conventional solvents of acetic acid and acetonitrile as the reaction solvent for the first time, and the solvent is simple and convenientTiO with continuous two-dimensional nano-sheet structure prepared by using hydrothermal method 2 The material has the advantages of mild reaction condition, simple process, strong controllability and good reproducibility, and no template or post-treatment step in the preparation process, and the prepared TiO 2 The material has wide application in the fields of solar cells, ion batteries, photocatalysis and the like.
Drawings
FIG. 1 is a diagram of TiO prepared in example 1 2 SEM image of the material.
FIG. 2 is a diagram showing TiO as prepared in comparative example 1 2 SEM image of the material.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Mixing 10mL of acetic acid and 40mL of acetonitrile uniformly, adding 2mL of tetra-n-butyl titanate, stirring uniformly, adding into a reaction kettle, performing solvothermal reaction at 200 ℃ for 16h, naturally cooling, centrifuging, washing and drying to obtain the TiO with a continuous two-dimensional nano-sheet structure 2 The thickness of the material, nano-sheet is 10-15nm.
Example 2
Mixing 20mL of acetic acid and 30mL of acetonitrile uniformly, adding 2mL of tetra-n-butyl titanate, stirring uniformly, adding into a reaction kettle, performing solvothermal reaction at 200 ℃ for 16h, naturally cooling, centrifuging, washing and drying to obtain the TiO with a continuous two-dimensional nano-sheet structure 2 The thickness of the material, nano-sheet is 10-15nm.
Example 3
Adding 2mL of tetrabutyl titanate into 50mL of organic solvent (wherein the organic solvent is formed by mixing acetic acid and acetonitrile according to the volume ratio of 1:1), uniformly stirring, adding into a reaction kettle, performing solvothermal reaction at 180 ℃ for 24 hours, naturally cooling, centrifuging, washing and drying to obtain the TiO with a continuous two-dimensional nano-sheet structure 2 The thickness of the material, nano-sheet is 10-15nm.
Example 4
25mL of acetic acid and 25mL of acetonitrile are mixed uniformly, then 2mL of tetra-n-butyl titanate is added and stirred uniformlyAdding the mixture into a reaction kettle, performing solvothermal reaction for 12 hours at 220 ℃, naturally cooling, centrifuging, washing and drying to obtain the TiO with a continuous two-dimensional nano-sheet structure 2 The thickness of the material, nano-sheet is 10-15nm.
Comparative example 1
Mixing 5mL of acetic acid and 45mL of acetonitrile uniformly, adding 2mL of tetra-n-butyl titanate, stirring uniformly, adding into a reaction kettle, performing solvothermal reaction at 200 ℃ for 16h, naturally cooling, centrifuging, washing and drying to obtain TiO 2 A material.
FIG. 1 is a TiO prepared in example 1 2 The material can be seen to have a continuous two-dimensional nano-sheet structure with a nano-sheet thickness of 10-15nm. FIG. 2 is a TiO prepared in comparative example 1 2 A material, as can be seen, consisting of nanoparticles and irregular microspheres, the nanoparticle size<100nm, and the diameter of the microsphere is 1-2 mu m.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (1)
1. TiO with continuous two-dimensional nano sheet structure 2 A method of preparing a material comprising: uniformly mixing a titanium source and an organic solvent, and performing solvothermal reaction for 12-24 hours at 180-220 ℃ to obtain TiO 2 A material; the organic solvent is prepared from acetic acid and acetonitrile according to a volume ratio of 1: (1-4); the titanium source is tetrabutyl titanate, tetraisopropyl titanate or a combination thereof;
the TiO 2 The material is formed by continuous two-dimensional TiO 2 Nanoplatelets of the two-dimensional TiO 2 The thickness of the nano-sheet is 10-15nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111263396.5A CN113998733B (en) | 2021-10-28 | 2021-10-28 | TiO with continuous two-dimensional nano sheet structure 2 Method for producing materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111263396.5A CN113998733B (en) | 2021-10-28 | 2021-10-28 | TiO with continuous two-dimensional nano sheet structure 2 Method for producing materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113998733A CN113998733A (en) | 2022-02-01 |
| CN113998733B true CN113998733B (en) | 2023-12-05 |
Family
ID=79924599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111263396.5A Active CN113998733B (en) | 2021-10-28 | 2021-10-28 | TiO with continuous two-dimensional nano sheet structure 2 Method for producing materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113998733B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1749172A (en) * | 2004-09-15 | 2006-03-22 | 中国科学院合肥物质科学研究院 | The preparation method of titanium dioxide nano mesoporous balls |
| JP2006290680A (en) * | 2005-04-11 | 2006-10-26 | National Institute Of Advanced Industrial & Technology | Spherical nanoparticle porous body and method for synthesizing the same |
| CN103896330A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海硅酸盐研究所 | Modified titanium dioxide, preparation method thereof and solar cell prepared thereby |
| CN104787800A (en) * | 2015-04-14 | 2015-07-22 | 济南大学 | Flower-ball-shaped titanium dioxide and preparation method thereof |
| CN105399140A (en) * | 2015-11-26 | 2016-03-16 | 遵义医学院 | Preparation method for anatase nano TiO2 by using titanium tetrachloride-acetonitrile as intermediate |
| CN107278198A (en) * | 2014-12-23 | 2017-10-20 | 埃西勒国际通用光学公司 | A kind of continuous current method for being used to manufacture the metal oxide nanoparticles that surface is modified by supercritical solvent thermal synthesis |
| CN110124701A (en) * | 2019-06-25 | 2019-08-16 | 泉州师范学院 | A kind of preparation method and applications of molybdenum disulfide quantum dot/titanium dioxide nanoplate composite photo-catalyst |
| WO2019195916A1 (en) * | 2018-04-13 | 2019-10-17 | Nanophyll Inc. | Self-cleaning and anti-fouling graphene oxide/tio2 photoactive coating and large scale bonding-to- surface process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192900B (en) * | 2014-08-20 | 2016-05-11 | 北京师范大学 | A kind of TiO2Nanocrystalline synthetic method |
-
2021
- 2021-10-28 CN CN202111263396.5A patent/CN113998733B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1749172A (en) * | 2004-09-15 | 2006-03-22 | 中国科学院合肥物质科学研究院 | The preparation method of titanium dioxide nano mesoporous balls |
| JP2006290680A (en) * | 2005-04-11 | 2006-10-26 | National Institute Of Advanced Industrial & Technology | Spherical nanoparticle porous body and method for synthesizing the same |
| CN103896330A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海硅酸盐研究所 | Modified titanium dioxide, preparation method thereof and solar cell prepared thereby |
| CN107278198A (en) * | 2014-12-23 | 2017-10-20 | 埃西勒国际通用光学公司 | A kind of continuous current method for being used to manufacture the metal oxide nanoparticles that surface is modified by supercritical solvent thermal synthesis |
| CN104787800A (en) * | 2015-04-14 | 2015-07-22 | 济南大学 | Flower-ball-shaped titanium dioxide and preparation method thereof |
| CN105399140A (en) * | 2015-11-26 | 2016-03-16 | 遵义医学院 | Preparation method for anatase nano TiO2 by using titanium tetrachloride-acetonitrile as intermediate |
| WO2019195916A1 (en) * | 2018-04-13 | 2019-10-17 | Nanophyll Inc. | Self-cleaning and anti-fouling graphene oxide/tio2 photoactive coating and large scale bonding-to- surface process thereof |
| CN110124701A (en) * | 2019-06-25 | 2019-08-16 | 泉州师范学院 | A kind of preparation method and applications of molybdenum disulfide quantum dot/titanium dioxide nanoplate composite photo-catalyst |
Non-Patent Citations (2)
| Title |
|---|
| TiO_2薄膜优化对染料敏化太阳电池性能的影响;奚小网;胡林华;方霞琴;戴松元;;无机化学学报(第07期);全文 * |
| 介孔二氧化钛功能纳米材料的合成与应用;胡金林;杨其浩;陈静;王太亚;林鹤;钱海生;;化学进展(第12期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113998733A (en) | 2022-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101781459B (en) | Graphene/polyaniline conductive composite material and preparation method thereof | |
| CN102335605B (en) | Method for preparing copper-titanium dioxide core-shell nanoparticles | |
| CN103357425B (en) | Preparation method of molybdenum disulfide/titanium dioxide composite material with nano thorn hierarchical structure | |
| CN102769123B (en) | Preparation method of titanium dioxide/carbon composite lithium battery electrode material | |
| CN101781458A (en) | Graphene -organic acid doped polyaniline composite material and preparation method thereof | |
| CN107262116B (en) | Hierarchical structure MoS2/Cu2S composite material and preparation method thereof | |
| CN1725530A (en) | Preparation method of spinel lithium titanate nano tube/wire for lithium battery and capacitor | |
| CN106856241A (en) | A kind of multiphase composite nanostructure negative material and preparation method thereof | |
| CN103301860A (en) | Preparation method of multiwalled carbon nanotube supported silver phosphate visible light photocatalyst | |
| CN110707301A (en) | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof | |
| CN103059343B (en) | Modified carbon nanotube and preparation method thereof | |
| CN110611008B (en) | Preparation method of anti-reflection coating of solar cell | |
| CN102486967A (en) | Preparation method of composite ordered porous nanometer titanium dioxide (TiO2) film | |
| CN104787800A (en) | Flower-ball-shaped titanium dioxide and preparation method thereof | |
| CN111234525A (en) | Preparation method of doped polyaniline/nanocrystalline cellulose composite material | |
| CN105778088B (en) | A kind of graphene/polyaniline nanometer stick array composite and preparation method and application | |
| CN113998733B (en) | TiO with continuous two-dimensional nano sheet structure 2 Method for producing materials | |
| CN109928421A (en) | With flower-like micro/nano structure Zinc oxide powder and its preparation method and application | |
| CN104610575A (en) | Zinc-aluminum layered double hydroxide coated carbon nanotube composite powder and preparation method thereof | |
| CN105198004A (en) | Fe3O4-SnO2 nanometer composite and preparation method thereof | |
| CN109772241A (en) | A kind of nanoscale lignin-base microballoon and preparation method thereof | |
| CN113559856B (en) | Preparation method of barium titanate/silver iodate heterojunction photocatalyst | |
| CN108295903A (en) | A kind of cadmiumsulfide quantum dot-phthalein mountain valley with clumps of trees and bamboo bronzing catalyst and preparation method for hydrogen manufacturing | |
| CN113101952B (en) | Bi 4 O 5 I 2 /Bi 5 O 7 I composite photocatalyst and preparation method and application thereof | |
| CN112875757A (en) | Design and synthesis method of manganese molybdate nanowire/graphene composite material for supercapacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 |