CN110015693B - Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material - Google Patents

Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material Download PDF

Info

Publication number
CN110015693B
CN110015693B CN201910258729.1A CN201910258729A CN110015693B CN 110015693 B CN110015693 B CN 110015693B CN 201910258729 A CN201910258729 A CN 201910258729A CN 110015693 B CN110015693 B CN 110015693B
Authority
CN
China
Prior art keywords
ammonia
dimensional amorphous
moo
amorphous moo
gel precursor
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
CN201910258729.1A
Other languages
Chinese (zh)
Other versions
CN110015693A (en
Inventor
王志江
戴丁
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.)
Harbin Institute of Technology
Original Assignee
Harbin Institute 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 Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201910258729.1A priority Critical patent/CN110015693B/en
Publication of CN110015693A publication Critical patent/CN110015693A/en
Application granted granted Critical
Publication of CN110015693B publication Critical patent/CN110015693B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a two-dimensional amorphous MoO with high-efficiency electrocatalysis of ammonia from nitrogenxA method of preparing a material, the method comprising the steps of: s1: dissolving inorganic salt containing molybdenum ions and organic acid in deionized water to form a uniform solution; adding an organic alcohol solvent into the solution while stirring, adjusting the pH value to be neutral by using weak base, and heating the obtained homogeneous suspension by using an oil bath to obtain a gel precursor; s2: putting the gel precursor into a crucible, transferring the gel precursor into a tube furnace, and burning the gel precursor in a gas atmosphere; s3: after cooling to room temperature, collecting the burned two-dimensional amorphous MoO from the tube furnacexA material. The invention utilizes the rapid 'glue blowing' technology to prepare the two-dimensional amorphous MoOxThe material has the advantages of simple preparation, low cost, large specific surface area, increased active sites of reaction and high electron transmission efficiency, thereby greatly improving the efficiency of the electrocatalytic ammonia synthesis reaction.

Description

Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material
Technical Field
The invention belongs to the technical field of new material field, and relates to a method for reducing nitrogen in the atmosphere into ammonia (NH) at room temperature and normal pressure3) Of two-dimensional amorphous MoOxThe green preparation method of (1).
Background
N2The reserves in the earth's atmosphere are abundant, 78% of the air is nitrogen, but most animals and plants cannot directly utilize the free nitrogen, and only reduce and convert the nitrogen into NH3Can be utilized. Ammonia, as an important chemical, plays an important role in the global industry, industrially every yearProducing about 1.5 million tons of ammonia, consuming about 2% of the total energy reserve. NH over a hundred years3The production uses the Haber-Bosch process, and the annual yield of ammonia synthesized by the method is about 108And each ton accounts for about 20-25% of the ammonia consumed by the earth all the year. This process requires heating the nitrogen and hydrogen molecules to about 400 deg.C and pressurizing to about 150-350 atm, while an iron-based catalyst is required to promote ammonia gas generation.
N2 + 3H2→2NH3
Although this reaction is exothermic, higher temperatures are required to accelerate the reaction kinetics. However, this shifts the equilibrium towards the reactants, reducing the conversion, which can only be relieved by increasing the pressure, with a conversion of ammonia of only 10-15% throughout the process. This process consumes a large amount of hydrogen and energy, which are derived from the combustion of fossil fuels, and undoubtedly increases the carbon emission, and burdens resources and the environment. Thus establishing green and environmentally sustainable NH3The production strategy is of great significance. The reduction of nitrogen to ammonia by electrochemical catalysis is an environmentally friendly ammonia production process and one of the promising options in the energy and chemical industry.
The electrochemical synthesis method of ammonia can take nitrogen and water as raw materials at normal temperature and normal pressure, and reduce the nitrogen into ammonia by applying voltage. The method has the advantages of simple equipment, easily obtained raw materials, low energy consumption and less pollution, thereby being widely concerned. However, the current electrochemical method for synthesizing ammonia is not put into industrial use, mainly because the conversion rate needs to be improved, and the search for a high-efficiency and stable catalyst is one of the key points of the technical development.
Two-dimensional nanomaterials are a recent research hotspot, and because of their unique electronic transmission characteristics, large specific surface area, rapid ion transmission and other advantages, they provide opportunities for basic and technical research in various fields including catalysis, energy storage, sensing and electronic devices such as field effect transistors and logic circuits.
Disclosure of Invention
The invention provides a high-efficiency electrocatalysis for solving the current situation of shortage of high-efficiency synthetic ammonia catalystTwo-dimensional amorphous MoO with ammonia as nitrogenxA method for preparing the material. The invention utilizes the rapid 'glue blowing' technology to prepare the two-dimensional amorphous MoOxThe material has the advantages of simple preparation, low cost, large specific surface area, increased active sites of reaction and high electron transmission efficiency, thereby greatly improving the efficiency of the electrocatalytic ammonia synthesis reaction.
The purpose of the invention is realized by the following technical scheme:
two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxThe preparation method of the material comprises the following steps:
s1: dissolving inorganic salt containing molybdenum ions and organic acid in deionized water to form a uniform solution; adding an organic alcohol solvent into the solution while stirring, adjusting the pH value to be neutral by using weak base, and heating the obtained homogeneous suspension for 1-6 h at 50-120 ℃ by using an oil bath to obtain a gel precursor.
In this step, the molar ratio of the molybdenum ion to the organic acid is 1: 1-4, making the organic acid in an excessive state; the mass volume ratio of the organic acid to the deionized water is 1 g: 0.8-1.5 ml; the mass volume ratio of the organic acid to the organic alcohol solvent is 1 g: 0.9-1.4 ml; the inorganic salt containing molybdenum ions is one of ammonium molybdate, ammonium phosphomolybdate, ammonium heptamolybdate and the like; the organic acid is one of citric acid, salicylic acid or ethylenediamine tetraacetic acid and the like; the organic alcohol solvent is one of ethanol, glycol or glycerol; the weak base is one of ammonia water and the like.
S2: and putting the gel precursor into a crucible, transferring the gel precursor into a tube furnace, and burning for 10-120 min at 400-1200 ℃ in a gas atmosphere.
In this step, the gas atmosphere is an argon or nitrogen gas atmosphere.
S3: after cooling to room temperature, collecting the burned two-dimensional amorphous MoO from the tube furnacexThe material is not required to be washed in the step, and x is between 2 and 3.
Compared with the prior art, the invention has the following advantages:
1. two-dimensional amorphous MoO prepared by the inventionxMaterialThe raw materials are inorganic salt containing metal molybdenum ions, weak organic acid, organic alcohol solvent and weak base, firstly, a gel precursor is prepared through esterification crosslinking reaction, then, gel with high viscosity can be easily obtained through a liquid phase sol-gel process, a large amount of gas is contained in the gel, and a chemical blowing process can be generated through a rapid heating technology, so that the gel expands to generate two-dimensional nano flaky MoOxA material. The material is simple to prepare, has good performance, and can realize the reduction of ammonia (NH) as nitrogen in the atmosphere at room temperature and normal pressure3) The reaction rate of 6.8X 10 can be realized when the applied voltage is 0V relative to the standard hydrogen electrode-11mol/s/cm2And a faraday efficiency of 30.33%.
2. Two-dimensional amorphous MoO prepared by the inventionxThe material can be used as a catalyst for the electrocatalytic ammonia synthesis reaction, has good performance, and simultaneously the preparation method opens up a new way for economically preparing the two-dimensional nanosheet with high quality, high uniformity and large transverse dimension on a large scale.
Drawings
FIG. 1 is the MoO prepared in example 1xAn XRD pattern of (a);
FIG. 2 is the MoO prepared in example 1xSEM image of (a);
FIG. 3 is the MoO prepared in example 1xA TEM image of (a);
FIG. 4 is the MoO prepared in example 1xThe HRTEM image of (1);
FIG. 5 is the MoO prepared in example 1xXPS spectra of (a);
FIG. 6 is the MoO prepared in example 1xEDS spectra of (a);
FIG. 7 is a MoO prepared in example 1xSTEM images and element profiles of;
FIG. 8 is a MoO prepared in example 1xThe catalytic performance of (a) is an ammonia generation efficiency curve, and b is a reaction faradaic efficiency curve.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
Example 1:
in this example, a two-dimensional amorphous MoOxThe preparation method comprises the following four steps:
firstly, preparing a gel precursor: 45mmol ammonium molybdate and 94.68mmol ethylenediamine tetraacetic acid were weighed and dissolved in 25 ml deionized water to form a homogeneous solution, 32ml ethylene glycol was added to the solution with stirring, and NH was added thereto3·H2O, adjusting the pH value of the mixed solution to 7, and heating the obtained homogeneous suspension in an oil bath for 2 hours at the temperature of 80 ℃;
secondly, the process of 'quick glue blowing': putting the obtained gel into a crucible, quickly transferring the gel into a tubular furnace, and burning the gel for 30 min at 550 ℃ in Ar atmosphere;
and thirdly, after cooling to room temperature, collecting the product from the tube furnace without washing.
As can be seen from the fact that the XRD pattern of FIG. 1 is a steamed bread peak and the HRTEM image of FIG. 4 has no obvious lattice fringes, the MoO prepared by the embodiment has the advantages of high purity, high purity and good stabilityxThe material is in an amorphous state.
As is clear from the SEM image of FIG. 2 and the TEM image of FIG. 3, the MoO prepared in this examplexThe microscopic appearance of the material is a two-dimensional sheet structure.
As can be seen from the XPS spectrum of FIG. 5 and the EDS analysis spectrum of FIG. 6, MoO prepared in this examplexThe main constituent elements of the sample are Mo and O, and the distribution of the Mo and the O is shown in FIG. 7.
As can be seen from the performance test chart of FIG. 8, the MoO prepared in this examplexWhen the applied voltage of the material is 0V relative to the standard hydrogen electrode, the reaction generation rate and the Faraday efficiency are the highest and are respectively 6.8 multiplied by 10-11mol/s/cm2And 30.33%, excellent catalytic performance.
In the embodiment, a high-viscosity gel precursor is prepared by adopting a liquid-phase sol-gel process, and then the high-viscosity gel precursor is acted on by using a rapid heating technology, wherein the gel precursor is subjected to the processThe body undergoes strong oxidation-reduction reaction to generate flame and release a large amount of gas, and the gel precursor expands at the moment, so that the two-dimensional amorphous MoO is realizedxMass production of materials. The resulting two-dimensional amorphous MoOxThe material obtains a larger specific surface area. Therefore, compared with the traditional preparation method of the two-dimensional material, the preparation method is simple to operate, low in cost and capable of realizing large-scale industrial production; the raw materials used for preparation are simple and pollution-free, and the prepared product does not need further purification process; the reaction flexibility is high, the raw materials and the reaction conditions are variable, and different large-size uniform two-dimensional nanosheets can be obtained by adjusting the reaction conditions according to different actual requirements; the method is also applicable to non-layered materials, and breaks the limitation of the stripping method.
Example 2:
the present embodiment is different from embodiment 1 in that: in step one, 6.43mmol ammonium heptamolybdate and 45mmol citric acid were weighed.
Example 3:
the present embodiment is different from embodiment 1 in that: in step one, 32ml of ethanol was added to the solution with stirring.
Example 4:
the present embodiment is different from embodiment 1 in that: the homogeneous suspension obtained in step one was heated in an oil bath at 100 ℃ for 2 h.
Example 5:
the present embodiment is different from embodiment 1 in that: in the second step, the mixture is burned for 30 min at 550 ℃ in the nitrogen atmosphere.
Example 6:
the present embodiment is different from embodiment 1 in that: in the second step, the mixture is burned for 30 min at 650 ℃ in the argon atmosphere.

Claims (7)

1. Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxA method for the preparation of a material, characterized in that the method comprises the steps of:
s1: dissolving inorganic salt containing molybdenum ions and organic acid in deionized water to form a uniform solution; adding an organic alcohol solvent into the solution while stirring, adjusting the pH value to be neutral by using weak base, heating the obtained homogeneous suspension for 1-6 h at 50-120 ℃ by using an oil bath to obtain a gel precursor, wherein: the molar ratio of molybdenum ions to organic acid is 1: 1-4, wherein the mass volume ratio of the organic acid to the deionized water is 1 g: 0.8-1.5 ml, wherein the mass volume ratio of the organic acid to the organic alcohol solvent is 1 g: 0.9-1.4 ml;
s2: putting the gel precursor into a crucible, transferring the gel precursor into a tube furnace, and burning for 10-120 min at 400-1200 ℃ in a gas atmosphere;
s3: after cooling to room temperature, collecting the burned two-dimensional amorphous MoO from the tube furnacexA material.
2. The two-dimensional amorphous MoO of claim 1 for electrocatalytic high efficiency nitrogen-to-ammoniaxThe preparation method of the material is characterized in that the inorganic salt containing molybdenum ions is one of ammonium molybdate, ammonium phosphomolybdate and ammonium heptamolybdate.
3. The two-dimensional amorphous MoO of claim 1 for electrocatalytic high efficiency nitrogen-to-ammoniaxThe preparation method of the material is characterized in that the organic acid is one of citric acid, salicylic acid or ethylenediamine tetraacetic acid.
4. The two-dimensional amorphous MoO of claim 1 for electrocatalytic high efficiency nitrogen-to-ammoniaxThe preparation method of the material is characterized in that the organic alcohol solvent is one of ethanol, glycol or glycerol.
5. The two-dimensional amorphous MoO of claim 1 for electrocatalytic high efficiency nitrogen-to-ammoniaxThe preparation method of the material is characterized in that the weak base is ammonia water.
6. The two-dimensional amorphous MoO of claim 1 for electrocatalytic high efficiency nitrogen-to-ammoniaxThe preparation method of the material is characterized in that the gas atmosphere is argon or nitrogen.
7. The two-dimensional amorphous MoO of claim 1 for electrocatalytic high efficiency nitrogen-to-ammoniaxMethod for the production of a material, characterized in that the two-dimensional amorphous MoO isxIn the material, x is between 2 and 3.
CN201910258729.1A 2019-04-01 2019-04-01 Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material Active CN110015693B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910258729.1A CN110015693B (en) 2019-04-01 2019-04-01 Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910258729.1A CN110015693B (en) 2019-04-01 2019-04-01 Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material

Publications (2)

Publication Number Publication Date
CN110015693A CN110015693A (en) 2019-07-16
CN110015693B true CN110015693B (en) 2021-07-16

Family

ID=67190463

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910258729.1A Active CN110015693B (en) 2019-04-01 2019-04-01 Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material

Country Status (1)

Country Link
CN (1) CN110015693B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110699705A (en) * 2019-11-14 2020-01-17 哈尔滨工业大学 Preparation method of carbon-loaded Mo nanoparticle electrode and method for synthesizing ammonia by electrochemically reducing nitrogen by using carbon-loaded Mo nanoparticle electrode as working electrode
WO2024083850A1 (en) 2022-10-18 2024-04-25 ETH Zürich Electrocatalyst

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108910952A (en) * 2018-08-31 2018-11-30 厦门理工学院 A kind of foam-like molybdenum dioxide and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108910952A (en) * 2018-08-31 2018-11-30 厦门理工学院 A kind of foam-like molybdenum dioxide and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Electrochemical N2 fixation to NH3 under ambient conditions: Mo2N nanorod as a highly efficient and selective catalyst;Xiang Ren et al.;《 Chemical Communications》;20180704;第54卷;第8474-8477页及实验部分 *
Mass Production of Large-Sized，Nonlayered 2D Nanosheets：Their Directed Synthesis by a Rapid "Gel-Blowing"Strategy，and Applications in Li/Na Storage and Catalysis;Dong Wang et al.;《Advanced Materials》;20181025;第30卷(第43期);第1803569-1803579页及实验部分 *
MoO3 nanosheets for efficient electrocatalytic N2 fixation to NH3;Jingrui Han et al.;《Journal of Materials Chemistry A》;20180623;第6卷(第27期);第12974-12977页 *

Also Published As

Publication number Publication date
CN110015693A (en) 2019-07-16

Similar Documents

Publication Publication Date Title
US10702857B2 (en) Monatomic metal-doped few-layer molybdenum disulfide electrocatalytic material, preparing method thereof, and method for electrocatalytic nitrogen fixation
Wu et al. Biomass-derived oxygen-doped hollow carbon microtubes for electrocatalytic N 2-to-NH 3 fixation under ambient conditions
CN105839131A (en) Water electrolytic hydrogen production catalytic electrode of self-supporting metal-doped cobalt phosphide nano structure
CN106319559B (en) A kind of electro-catalysis hydrogen manufacturing material and preparation method thereof
CN109659143A (en) A kind of nickel hydroxide/three nickel of curing/foam nickel composite and the preparation method and application thereof
CN105107536A (en) Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis
CN111604048B (en) Method for synthesizing ammonia by electrocatalytic reduction of nitrogen and catalyst used in same
CN103303912A (en) Preparation method of high-specific-surface-area porous nitrogen-doped graphitizing carbon nanomaterial
CN106334501A (en) Three-dimensional N/S double-doped graphene aerogel as well as preparation method and application thereof
CN109989070B (en) Three-dimensional grading FeP nanosheet hydrogen evolution electro-catalytic material and preparation method and application thereof
CN107519905B (en) Vanadium carbide nano-sieve electrocatalytic material capable of being used in wide pH range and preparation method thereof
CN110015693B (en) Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material
He et al. Dual modulation of morphology and electronic structures of VN@ C electrocatalyst by W doping for boosting hydrogen evolution reaction
CN111036307B (en) Preparation method of composite efficient oxygen evolution catalyst
Zhou et al. Hetero-structured CoS2-MoS2 hollow microspheres with robust catalytic activity for alkaline hydrogen evolution
CN106637274A (en) neutral and nearly-neutral water oxidation catalytic electrodes in transition metal salt nano arrays
Shao et al. Continuous synthesis of few-layer MoS2 with highly electrocatalytic hydrogen evolution
Fan et al. Construction of efficient bismuth/boron-based flexible electrodes in organic media toward neutral hydrogen evolution
CN109806898B (en) Boron-nitrogen co-doped carbon material and preparation method and application thereof
CN108565469A (en) A kind of cobalt-nitrogen-doped carbon composite material and preparation method
CN110540196A (en) boron-nitrogen co-doped porous graphene and preparation method and application thereof
CN112316965B (en) Preparation method and application of composite material derived by loading molybdenum disulfide nanosheet based on laccase-copper phosphate nanoflowers as substrate
CN112853393B (en) Ferroferric oxide catalyst for electrochemically synthesizing ammonia and preparation method and application thereof
Dai et al. Enhancing green ammonia electrosynthesis through tuning Sn vacancies in Sn-based MXene/MAX hybrids
CN111905783B (en) Molybdenum carbide/carbon nano hydrogen production catalyst synthesized by using ink

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