CN112592490B - Metal organic framework material of polynuclear cobalt cluster based on two-head pyrazole ligand and application - Google Patents

Metal organic framework material of polynuclear cobalt cluster based on two-head pyrazole ligand and application Download PDF

Info

Publication number
CN112592490B
CN112592490B CN202011484322.XA CN202011484322A CN112592490B CN 112592490 B CN112592490 B CN 112592490B CN 202011484322 A CN202011484322 A CN 202011484322A CN 112592490 B CN112592490 B CN 112592490B
Authority
CN
China
Prior art keywords
bpz
metal
organic framework
pyrazole
atoms
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
Application number
CN202011484322.XA
Other languages
Chinese (zh)
Other versions
CN112592490A (en
Inventor
李建荣
何涛
孔祥婧
司广锐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN202011484322.XA priority Critical patent/CN112592490B/en
Publication of CN112592490A publication Critical patent/CN112592490A/en
Application granted granted Critical
Publication of CN112592490B publication Critical patent/CN112592490B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers

Abstract

A multinuclear cobalt cluster metal organic framework material based on two-end pyrazole ligands and application thereof belong to the technical field of crystalline materials. Chemical formula is [ Co ]8(OH)4(OH2)2(BPZ‑X)6]，H2BPZ-X is aryl di (1H-pyrazole), X represents an aromatic ring, and X is Pd, Pz and Pm and is pyridazinyl, pyrazinyl and pyrimidinyl respectively. The synthesis condition of the metal-organic framework is that in a closed environment, an organic ligand aryl di (1H-pyrazole) (H)2BPZ-X) and cobalt nitrate in a mixed solution of N, N-dimethylformamide and water to obtain a crystal of the metal organic framework material through a solvothermal reaction; the metal-organic framework material shows separation performance to propylene/propyne mixed gas.

Description

Metal organic framework material of polynuclear cobalt cluster based on two-head pyrazole ligand and application
Technical Field
The invention belongs to the technical field of crystalline materials, and relates to a metal-organic coordination polymer material, which is characterized by a multinuclear cobalt cluster metal-organic framework material, a preparation method thereof and low-carbon hydrocarbon separation performance research.
Background
Metal-Organic Frameworks (MOFs), for short, are formed by the connection of Metal ions or Metal clusters and Organic ligands through coordination bonds. Compared with the traditional porous materials such as zeolite and activated carbon, the MOF has the characteristics of various structures, high order, good designability, easy functionalization and the like, and has wide application prospects in a plurality of research fields such as gas storage, separation, catalysis, sensing and the like.
The pore size and pore surface of MOFs can be controlled and can be used for alkane separation, and also due to chiral separation, the application in this respect is expanding. The mechanism of the MOF material for gas separation is generally based on the difference of the size, shape, polarity, polarizability and coordination ability of guest molecules, and the MOF material can produce differential adsorption to each component in the mixture. However, the existing porous materials have low adsorption selectivity to important industrial mixtures, and are still difficult to perform efficient separation and purification under mild conditions. The series of metal organic frameworks obtained by the invention can realize the separation of the propylene/propyne mixed gas under the mild condition.
Disclosure of Invention
The invention aims to provide a multinuclear cobalt cluster metal organic framework material based on two pyrazole ligands, a preparation method thereof and application of the metal organic framework material in low-carbon hydrocarbon separation performance research.
The invention relates to a metal-organic framework material of a polynuclear cobalt cluster based on two-head pyrazole ligand, and the chemical molecular formula is [ Co ]8(OH)4(OH2)2(BPZ-X)6]，H2BPZ-X is aryl di (1H-pyrazole), X represents aromatic heterocycle, X is Pd, Pz, Pm, and is pyridazinyl, pyrazinyl, pyrimidinyl respectively;
from the perspective of frame connection construction, the crystal structure of the metal-organic frame belongs to a cubic crystal system, and the space group is Fm-3 m.
The asymmetric unit of the metal-organic framework crystal structure has one crystallographically independent Co atom and 1/2 BPZ-X atoms2-A ligand. The Co atom coordinates six atoms in a double-retro-tetrahedral configuration, the coordinating atoms including three N atoms and three O atoms, wherein the three N atoms are derived from three different BPZ-X atoms2-The pyrazole group of the ligand and the three O atoms come from the water molecules of the reaction system. Eight adjacent Co atoms passing through six μ4-OH/OH2Joined together to form an eight-core Co8(μ4-OH)2(μ4-OH2)4MetalCluster (Co)8O6). Each Co8O6Cluster-connected twelve BPZ-X2-Ligands, each ligand bridging two Co8O6The metal clusters, ligands and metal clusters are alternately connected to form a three-dimensional framework.
In the metal-organic framework, the bond length of the Co-N bond is within
Figure BDA0002838580740000021
In the range of the bond length of Co-O bond
Figure BDA0002838580740000022
Within the range. Each BPZ-X2-Ligands bridge two Co8O6Cluster of each Co8O6Clusters and twelve crystallographically equivalent BPZ-X2-And (3) connecting ligands to respectively form a tetrahedral cage and an octahedral cage, and stacking the two cage-shaped structures to form a three-dimensional frame.
From a topological perspective, each BPZ-X2-The ligands can all be regarded as one-sided, twelve-coordinated Co8Secondary Building Units (SBUs) are treated as 12-connected vertices, and the two types of building units are alternately connected to form a classical fcu network.
The synthesis method of the metal-organic framework material comprises the following steps:
aryl bis (1H-pyrazole) (H) under sealed conditions2BPZ-X) is a catalyst of cobalt nitrate (Co (NO)3)2·6H2O) in a mixed solution of N, N-Dimethylformamide (DMF) and deionized water, to obtain crystals of the metal-organic framework via a solvothermal reaction.
Further preferred is the organic ligand arylbis (1H-pyrazole) (H)2The molar ratio of BPZ-X) to cobalt nitrate is 1 (1-4), each 0.05mmol of nickel nitrate corresponds to 1-4 mL of DMF and 0.1-4 mL of deionized water, the temperature of the thermal reaction is 100-160 ℃, and the reaction time is 12-60 hours.
The metal-organic framework has better chemical stability, so that the MOFs can be used for separating propylene/propyne mixed gas under the environmental condition.
Drawings
FIG. 1 is a structural diagram of two-end pyrazole ligands used for constructing such metal-organic frameworks.
FIG. 2 shows two-terminal pyrazole ligands H for synthesizing the metal-organic framework2Synthetic scheme for BPZ-Pd.
FIG. 3 is a diagram of the inorganic building blocks of the metal-organic framework.
Fig. 4 is a schematic three-dimensional structure of the metal-organic framework.
Fig. 5 is an adsorption isotherm diagram of the metal-organic framework material on propylene and propyne.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
weighing ligand H2BPZ-Pd (0.06mmoL) and Co (NO)3)2·6H2O (0.12mmoL) was placed in a 20mL beaker, 10mL of DMF solution and 2mL of deionized water were added, the beaker was placed in an ultrasonic apparatus and sonicated at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reaction vessel. After sealing, the reaction kettle is placed in a 110 ℃ oven for reaction for 24 hours. After the reaction is finished, closing the oven, cooling to room temperature, opening the reaction kettle, filtering the product obtained in the reaction kettle, collecting solid particles, and sequentially using DMF (dimethyl formamide) and H (hydrogen peroxide) to obtain the product2Washed with O and EtOH (5 mL. times.3) and observed under a microscope to give yellow octahedral crystals (Co)8(OH)4(OH2)2(BPZ-Pd)6) (yield: 43% based on H2BPZ-Pd ligand).
Example 2:
weighing ligand H2BPZ-Pz (0.06mmoL) and Co (NO)3)2·6H2O (0.12mmoL) was placed in a 20mL beaker, 10mL of DMF solution and 2.5mL of deionized water were added, and the beaker was placed in an sonicator and sonicated at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reaction vessel. After sealing, the reaction kettle is placed in an oven at 105 ℃ for reaction for 48 hours. After the reaction is finished, the oven is closed and cooledCooling to room temperature, opening the reaction kettle, filtering the product obtained in the reaction kettle, collecting solid particles, and sequentially adding DMF (dimethyl formamide) and H (hydrogen peroxide) into the obtained product2Washed with O and EtOH (5 mL. times.3) and observed under a microscope to give yellow octahedral crystals (Co)8(OH)4(OH2)2(BPZ-Pz)6) (yield: 49% based on H2BPZ-Pz ligand).
Example 3
Weighing ligand H2BPZ-Pm (0.06mmoL) and Co (NO)3)2·6H2O (0.12mmoL) was placed in a 20mL beaker, 10mL of DMF solution and 0.5mL of deionized water were added, and the beaker was placed in an sonicator and sonicated at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reaction vessel. After sealing, the reaction kettle is placed in an oven at 120 ℃ for reaction for 48 hours. After the reaction is finished, closing the oven, cooling to room temperature, opening the reaction kettle, filtering the product obtained in the reaction kettle, collecting solid particles, and sequentially using DMF (dimethyl formamide) and H (hydrogen peroxide) to obtain the product2Washed with O and EtOH (5 mL. times.3) and observed under a microscope to give yellow octahedral crystals (Co)8(OH)4(OH2)2(BPZ-Pm)6) (yield: 37% based on H2BPZ-Pm ligand).
Example 4
Weighing ligand H2BPZ-Pm (0.04mmoL) and Co (NO)3)2·6H2O (0.1mmoL) was placed in a 20mL beaker, 8mL of DMF solution and 0.3mL of deionized water were added, and the beaker was placed in an ultrasonic apparatus and sonicated at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reaction vessel. After sealing, the reaction kettle is placed in an oven at 130 ℃ for reaction for 48 hours. After the reaction is finished, closing the oven, cooling to room temperature, opening the reaction kettle, filtering the product obtained in the reaction kettle, collecting solid particles, and sequentially using DMF (dimethyl formamide) and H (hydrogen peroxide) to obtain the product2Washed with O and EtOH (5 mL. times.3) and observed under a microscope to give yellow octahedral crystals (Co)8(OH)4(OH2)2(BPZ-Pm)6) (yield: 47% based on H2BPZ-Pm ligand).
The test results of the products obtained in the above examples are the same, and specifically the following are given:
(1) determination of crystal structure:
selecting a single crystal sample with a proper size, and collecting data by using a Rigaku Supernova single crystal instrument at room temperature. Data collection Using Cu-Ka monochromated by graphite monochromator
Figure BDA0002838580740000041
A target ray. Data absorption correction was done using SCALE3 absack software. The crystal structure was resolved by direct methods using the program SHELXTL-97. Firstly, determining all non-hydrogen atom coordinates by using a difference function method and a least square method, obtaining the hydrogen atom position by using a theoretical hydrogenation method, and then refining the crystal structure by using SHELXTL-97. The structure is shown in fig. 3 to 4. The crystallographic data are shown in table 1.
TABLE 1 crystallography data for metal organic framework materials
Figure BDA0002838580740000051
Figure BDA0002838580740000061
FIG. 1 is a structural diagram of two-end pyrazole ligands used for constructing such metal-organic frameworks.
FIG. 2 shows two-terminal pyrazole ligands H for synthesizing the metal-organic framework2The BPZ-X (X ═ Pd, Pz, Pm) roadmap indicates: firstly, dibromoaryl and tetrahydropyrane protected pyrazole boric acid ester are added into 1, 4-dioxane and water, potassium carbonate and tetrakis (triphenylphosphine) palladium are added, sealing and vacuumizing are carried out, inert gas is used for protection, and heating reaction is carried out to obtain bis (1- (tetrahydro-2H-pyran-2-yl) -1H-pyrazole-4-yl) aryl; then bis (1- (tetrahydro-2H-pyran-2-yl) -1H-pyrazol-4-yl) aryl is heated and deprotected in ethanol solution of hydrochloric acid to obtain bis (1H-pyrazol-4-yl) aryl.
FIG. 3 is a diagram of the inorganic building blocks of the metal-organic framework showing: the inorganic node contained in the frame structure is cubic Co8(μ4-OH)(μ4-OH2) A metal cluster.
Fig. 4 is a schematic three-dimensional structure of the metal-organic framework showing: the framework structure comprises octahedral and tetrahedral cages.
(2) Characterization of adsorption properties of low-carbon hydrocarbon compounds
Fig. 5 is an adsorption isotherm diagram of the metal-organic framework material on propylene and propyne, and it can be seen that the material has obvious difference in adsorption behaviors on propylene and propyne, and can be used for adsorption separation of propylene/propyne mixed gas. FIG. 5 is an adsorption isotherm of propylene and propyne in a thermostatic waterbath at 298K for the material of the present invention, as tested by a gas adsorber.

Claims (3)

1. A metal-organic framework material based on two-end pyrazole ligand is characterized in that the chemical formula is [ Co ]8(OH)4(OH2)2(BPZ-X)6]，H2BPZ-X is aryl di (1H-pyrazole), X represents an aromatic ring, and X is Pd, Pz and Pm and is pyridazinyl, pyrazinyl and pyrimidinyl respectively;
H2the three internal structures of BPZ-X are as follows:
Figure FDA0003503711420000011
the metal-organic framework has the same framework structure, and from the perspective of framework connection construction, the crystal structure of the metal-organic framework belongs to a cubic crystal system, and the space group is Fm-3 m;
the asymmetric unit of the metal-organic framework crystal structure has one crystallographically independent Co atom and 1/2 BPZ-X atoms2-A ligand; the Co atom coordinates six atoms in a double-retro-tetrahedral configuration, the coordinating atoms including three N atoms and three O atoms, wherein the three N atoms are derived from three different BPZ-X atoms2-Pyrazole group of ligand, three O atoms come from water molecule of reaction system; eight adjacent Co atoms passing through six μ4-OH/OH2Joined together to form an eight-core Co8(μ4-OH)2(μ4-OH2)4Metal cluster (Co)8O6) (ii) a Each Co8O6Cluster-connected twelve BPZ-X2-Ligands, each ligand bridging two Co8O6The metal clusters, the ligands and the metal clusters which are alternately connected form a three-dimensional framework;
in the metal-organic framework, the bond length of the Co-N bond is within
Figure FDA0003503711420000012
In the range of the bond length of Co-O bond
Figure FDA0003503711420000013
Within the range; each BPZ-X2-Ligands bridge two Co8O6Cluster of each Co8O6Clusters and twelve crystallographically equivalent BPZ-X2-Ligand connection is carried out to respectively form a tetrahedral cage and an octahedral cage, and two cage-shaped structures are stacked to form a three-dimensional frame;
from a topological perspective, each BPZ-X2-The ligands can all be regarded as one-sided, twelve-coordinated Co8The secondary building units SBUs are considered as 12-connected vertices, and the two types of building units are alternately connected to form a classical fcu network.
2. A method for preparing a class of metal-organic framework materials based on bipitch pyrazole ligands according to claim 1, characterized in that arylbis (1H-pyrazole) H is prepared under sealed conditions2BPZ-X is a catalyst of cobalt nitrate Co (NO)3)2·6H2Obtaining the crystal of the metal-organic framework through solvothermal reaction of O in a mixed solution of N, N-Dimethylformamide (DMF) and deionized water; organic ligand aryl bis (1H-pyrazole) (H)2The molar ratio of BPZ-X) to cobalt nitrate is 1 (1-4), each 0.05mmol of nickel nitrate corresponds to 1-4 mL of DMF and 0.1-4 mL of deionized water, the temperature of the thermal reaction is 100-160 ℃, and the reaction time is 12-60 hours.
3. Use of a class of metal-organic framework materials based on double-headed pyrazole ligands according to claim 1 for selective adsorptive separation of propylene/propyne mixed gases.
CN202011484322.XA 2020-12-15 2020-12-15 Metal organic framework material of polynuclear cobalt cluster based on two-head pyrazole ligand and application Active CN112592490B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011484322.XA CN112592490B (en) 2020-12-15 2020-12-15 Metal organic framework material of polynuclear cobalt cluster based on two-head pyrazole ligand and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011484322.XA CN112592490B (en) 2020-12-15 2020-12-15 Metal organic framework material of polynuclear cobalt cluster based on two-head pyrazole ligand and application

Publications (2)

Publication Number Publication Date
CN112592490A CN112592490A (en) 2021-04-02
CN112592490B true CN112592490B (en) 2022-03-29

Family

ID=75196258

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011484322.XA Active CN112592490B (en) 2020-12-15 2020-12-15 Metal organic framework material of polynuclear cobalt cluster based on two-head pyrazole ligand and application

Country Status (1)

Country Link
CN (1) CN112592490B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112608492B (en) * 2020-12-29 2022-05-27 北京工业大学 Metal organic framework material of cobalt chain based on double-end pyrazole ligand, preparation and benzene adsorption application
CN115028850B (en) * 2022-06-09 2023-05-12 同济大学 Metal organic framework material for adsorbing and separating acetylene/ethylene mixed gas and preparation method thereof
CN115160585B (en) * 2022-07-26 2023-08-22 陕西师范大学 Metal organic framework fixed multi-core metal cluster material and preparation method and application thereof
CN116063691A (en) * 2023-01-06 2023-05-05 四川轻化工大学 Cobalt transition metal coordination polymer and preparation method and application thereof
CN117126419B (en) * 2023-10-26 2024-01-02 德州学院 Cobalt metal organic framework crystal material for gas separation and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104803818A (en) * 2015-03-27 2015-07-29 中国石油大学(北京) Method for liquid-phase ethylene oligomerization and polymerization in existence of metal organic framework material
CN110016145A (en) * 2019-05-08 2019-07-16 北京工业大学 Porous organo-metallic skeleton material, preparation method and its adsorbing separation application
WO2020089630A1 (en) * 2018-10-31 2020-05-07 Imperial College Innovations Limited Metal complexes for promoting growth in a photosynthetic organism

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10441924B2 (en) * 2014-07-24 2019-10-15 King Abdullah University Of Science And Technology Fabrication of highly CO2 selective metal-organic framework membrane using liquid phase epitaxy approach

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104803818A (en) * 2015-03-27 2015-07-29 中国石油大学(北京) Method for liquid-phase ethylene oligomerization and polymerization in existence of metal organic framework material
WO2020089630A1 (en) * 2018-10-31 2020-05-07 Imperial College Innovations Limited Metal complexes for promoting growth in a photosynthetic organism
CN110016145A (en) * 2019-05-08 2019-07-16 北京工业大学 Porous organo-metallic skeleton material, preparation method and its adsorbing separation application

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Co-7-Cluster-Based Metal-Organic Frameworks with Mixed Carboxylate and Pyrazolate Ligands: Construction and CO2 Adsorption and Fixation;Bian, ZX等;《CRYSTAL GROWTH & DESIGN》;20201202;第20卷(第12期);第7972-7978页 *
Structural Differences of Two MOFs Adjusted by Central Metal Ions Inducing Different Photodegradation Efficiencies;Li, HJ等;《CHINESE JOURNAL OF INORGANIC CHEMISTRY》;20180310;第34卷(第3期);第560-568页 *
基于含氮羧酸配体/Co2+构筑的2D层状配合物的合成及结构表征;王真玉等;《兴义民族师范学院学报》;20200430(第2期);第120-124页 *
由氢键连接的三个金属-有机网状化合物的合成、结构及半导体性质（英文）;陈飞剑等;《无机化学学报》;20160710(第07期);第1275-1282页 *

Also Published As

Publication number Publication date
CN112592490A (en) 2021-04-02

Similar Documents

Publication Publication Date Title
CN112592490B (en) Metal organic framework material of polynuclear cobalt cluster based on two-head pyrazole ligand and application
Waitschat et al. Flow-synthesis of carboxylate and phosphonate based metal–organic frameworks under non-solvothermal reaction conditions
CN109824910B (en) Nickel metal organic framework material based on three-head pyrazole ligand, and preparation method and application thereof
Lyndon et al. Tuning the structures of metal–organic frameworks via a mixed-linker strategy for ethylene/ethane kinetic separation
CN111100149B (en) Having a structure of C2H2And CH4Metal organic framework material with adsorption separation function and preparation method thereof
CN110016145B (en) Porous metal-organic framework material, preparation method and adsorption separation application thereof
CN113019330A (en) Preparation of copper-based metal-organic framework material and acetylene/carbon dioxide separation application thereof
CN110270314B (en) Effectively separate CO in flue gas2Preparation method of naphthalimide Zn-MOF
CN110167948A (en) Crystal metal organic frame
CN115678027B (en) Nickel-based dual-ligand metal organic framework material, preparation method and application
Asghar et al. Ultrasonication treatment enhances MOF surface area and gas uptake capacity
CN113801337B (en) Metal organic framework material for adsorbing and separating ethylene and ethane and preparation method and application thereof
CN113214493B (en) Preparation of cobalt-based metal organic framework material and low-carbon hydrocarbon separation application thereof
CN108384020B (en) Metal organic framework containing uncoordinated tetrazole group and synthesis method and application thereof
CN112500582B (en) Multinuclear cobalt cluster metal organic framework material based on four-head pyrazole ligand, preparation and application
CN109851559B (en) Nickel metal organic framework material based on double-end pyrazole ligand, and preparation method and application thereof
CN112795023B (en) Ultra-stable metal organic framework material and preparation method and application thereof
Meng et al. Microporous Cu metal-organic framework constructed from V-shaped tetracarboxylic ligand for selective separation of C2H2/CH4 and C2H2/N2 at room temperature
CN110563957A (en) Preparation method and application of three-dimensional iron-based metal-organic framework
Yan et al. Efficient adsorption separation of xylene isomers in zeolitic imidazolate framework-67@ MCF hybrid materials
CN113881061B (en) Metal organic framework porous material and preparation method and application thereof
CN112625069B (en) Cobalt metal organic framework material based on pyrene tetrapyrazole ligand, preparation method and application thereof
CN110982084B (en) Zirconium metal organic framework material based on shortest porphyrin carboxylic acid ligand, preparation and application thereof
Kim et al. Solid-state phase transformations toward a metal-organic framework of 7-connected Zn 4 O secondary building units
CN113136035A (en) Green synthesis method and application of Cr-based metal organic complex catalytic material

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