CN111545197A - Ru-ZnO photocatalyst and preparation method and application thereof - Google Patents
Ru-ZnO photocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111545197A CN111545197A CN202010410522.4A CN202010410522A CN111545197A CN 111545197 A CN111545197 A CN 111545197A CN 202010410522 A CN202010410522 A CN 202010410522A CN 111545197 A CN111545197 A CN 111545197A
- Authority
- CN
- China
- Prior art keywords
- zno
- annealing
- methane
- photocatalyst
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 117
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000137 annealing Methods 0.000 claims abstract description 35
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims abstract description 23
- 150000003751 zinc Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000006479 redox reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000012360 testing method Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 148
- 239000011787 zinc oxide Substances 0.000 description 106
- 238000003756 stirring Methods 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 21
- 238000001035 drying Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000000227 grinding Methods 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000593 degrading effect Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
Abstract
The invention provides a Ru-ZnO photocatalyst and a preparation method and application thereof, belonging to the technical field of photocatalysts. The preparation method of the Ru-ZnO photocatalyst provided by the invention comprises the following steps: mixing zinc salt, oxalic acid and water, and carrying out precipitation reaction to obtain zinc oxalate; carrying out first annealing on the zinc oxalate to obtain ZnO; mixing the ZnO, ruthenium chloride and water, and carrying out redox reaction to obtain a precursor; and carrying out second annealing on the precursor to obtain the Ru-ZnO photocatalyst. The preparation method provided by the invention can obtain the Ru-ZnO photocatalyst which can efficiently catalyze and degrade methane under simulated sunlight and shows excellent performance of photocatalytic purification of low-concentration methane in air at normal temperature and normal pressure; the 0.1-Ru-ZnO photocatalyst shows good cycling stability in ten-cycle degradation tests.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a Ru-ZnO photocatalyst and a preparation method and application thereof.
Background
Methane is a colorless and odorless gas at normal temperature and pressure, and is a typical nonpolar molecule. The C-H bond energy in methane is as high as 434KJ/mol, so that methane is very stable at room temperature, difficult to adsorb and difficult to activate and degrade. The traditional method for degrading methane is generally to realize the catalytic oxidation of methane under high temperature conditions by using a noble metal catalyst. Although the method is efficient, the cost of the noble metal is too high, and the method for degrading methane at high temperature needs to be carried out at the temperature of over 800 ℃, under the condition, the noble metal nano catalyst is easy to aggregate and grow, so that the catalyst is inactivated; the noble metal catalyst is easy to catalyze and oxidize nitrogen to generate oxynitride under the condition of high temperature, thereby causing secondary pollution. From an economic and practical point of view, the traditional thermocatalytic method is difficult to be used for the treatment of methane in the atmosphere.
Fujishima and Honda utilized TiO since 19722Semiconductor photocatalysis has received wide attention in the energy and environmental fields since single crystal photodissociation of water. The semiconductor photocatalysis technology can completely oxidize and decompose pollutants in the atmosphere only by utilizing solar energy, does not form secondary pollutants, and has the advantages of environmental protection, so that the semiconductor photocatalysis technology has wide application prospect in catalyzing and degrading low-concentration methane in the atmosphere at normal temperature and normal pressure. Three conditions need to be met for semiconductor materials that photocatalytically degrade/convert methane: (1) the semiconductor absorbs sunlight to generate electron and hole pairs; (2) the electrons and holes are separated and migrate to the semiconductor surface; (3) electrons and holes migrating to the semiconductor surface and CH adsorbed on the semiconductor surface4A redox reaction occurs. Therefore, the required catalyst can absorb wider sunlight; electrons and holes on the surface of the catalyst are not easy to recombine; and has good adsorbability to methane.
At present, aboutActivation of methane C-H and oxidation studies of methane are mainly based on TiO2On a base semiconductor and a molecular sieve, the research mainly focuses on photocatalytic conversion and photocatalytic oxidation of high-concentration methane, and reports on photocatalytic oxidation of low-concentration methane are rare. And TiO2The band gap of the solar energy-absorbing material is 3.2eV, and the solar energy-absorbing material can only absorb 5% of ultraviolet light in sunlight, so that the full utilization of the solar energy is limited, and the efficiency of degrading methane by photocatalysis is reduced. And other catalysts such as: CeO (CeO)2，Ga2O3，MoO3，V2O5And the like, can not realize the photocatalytic oxidation of low-concentration methane at normal temperature and normal pressure. Further, the catalysts for activating methane C-H and oxidizing methane have a problem of poor cycle stability. Therefore, the development of efficient, good and stable photocatalyst which can degrade the methane with low concentration in the atmosphere at normal temperature and normal pressure has great application value.
Disclosure of Invention
The invention aims to provide a preparation method of a Ru-ZnO photocatalyst which is efficient, has good circulation stability and can degrade low-concentration methane in the atmosphere at normal temperature and normal pressure.
The invention provides a preparation method of a Ru-ZnO photocatalyst, which comprises the following steps:
(1) mixing zinc salt, oxalic acid and water, and carrying out precipitation reaction to obtain zinc oxalate;
(2) performing first annealing on the zinc oxalate obtained in the step (1) to obtain ZnO;
(3) mixing the ZnO obtained in the step (2) with ruthenium chloride and water, and carrying out redox reaction to obtain a precursor;
(4) and (4) carrying out second annealing on the precursor obtained in the step (3) to obtain the Ru-ZnO photocatalyst.
Preferably, the zinc salt in step (1) is zinc nitrate and/or zinc acetate.
Preferably, the mass ratio of the zinc salt to the oxalic acid in the step (1) is (1:1) - (1: 2).
Preferably, the temperature of the first annealing in the step (2) is 250 to 550 ℃.
Preferably, the time of the first annealing in the step (2) is 1-10 h.
Preferably, the mass ratio of the ruthenium element to ZnO in the ruthenium chloride in the step (3) is (0.05:100) to (1: 100).
Preferably, the temperature of the second annealing in the step (4) is 30-350 ℃.
Preferably, the time of the second annealing in the step (4) is 0-6 h.
The invention also provides the Ru-ZnO photocatalyst obtained by the preparation method of the technical scheme, which comprises a ZnO matrix and Ru loaded on the surface of the ZnO matrix.
The invention also provides the application of the Ru-ZnO photocatalyst obtained by the preparation method in the technical scheme in catalyzing and purifying methane in air, wherein the concentration of the methane in the air is 1 ppb-10000 ppm.
The invention provides a preparation method of a Ru-ZnO photocatalyst, which comprises the steps of mixing zinc salt, oxalic acid and water, and carrying out precipitation reaction to obtain zinc oxalate; carrying out first annealing on the zinc oxalate to obtain ZnO; mixing the ZnO, ruthenium chloride and water, and carrying out redox reaction to obtain a precursor; and carrying out second annealing on the precursor to obtain the Ru-ZnO photocatalyst. The Ru-ZnO photocatalyst prepared by the preparation method provided by the invention is beneficial to adsorbing methane in air, ZnO can absorb sunlight to generate electron and hole pairs, the electron and the hole are separated and transferred to the surface of a semiconductor, and the electron and the hole transferred to the surface of the semiconductor and CH adsorbed on the surface of ZnO4Oxidation-reduction reaction occurs, so that the photoelectrocatalysis efficiency is improved; the composition of ZnO and Ru forms a heterostructure, so that the Ru-ZnO photocatalyst has good cycling stability. Experimental results show that the 0.1-0.5-Ru-ZnO provided by the invention can efficiently catalyze and degrade methane under simulated sunlight, and shows excellent performance of photocatalytic purification of low-concentration methane in air; the 0.1-Ru-ZnO photocatalyst shows good cycling stability in ten-cycle degradation tests. Therefore, the Ru-ZnO catalyst provided by the invention has high-efficiency catalytic performance and circulation stability on low-concentration methane under simulated sunlight, namely, the photocatalytic purification is largeThe low-concentration methane in the gas has good photocatalytic activity and circulation stability.
Drawings
FIG. 1 is a diagram of the performance of Ru-ZnO catalysts prepared in examples 1-6 in different proportions for photocatalytic degradation of methane under simulated sunlight;
FIG. 2 is a graph showing the cyclic stability of the 0.1-Ru-ZnO catalyst prepared in example 1 in the catalytic degradation of methane under simulated sunlight.
Detailed Description
The invention aims to provide a preparation method of a Ru-ZnO photocatalyst which is efficient, has good circulation stability and can degrade low-concentration methane in the atmosphere at normal temperature and normal pressure.
In order to achieve the above object, the present invention provides a preparation method of a Ru-ZnO photocatalyst, comprising the steps of:
(1) mixing zinc salt, oxalic acid and water, and carrying out precipitation reaction to obtain zinc oxalate;
(2) performing first annealing on the zinc oxalate obtained in the step (1) to obtain ZnO;
(3) mixing the ZnO obtained in the step (2) with ruthenium chloride and water, and carrying out redox reaction to obtain a precursor;
(4) and (4) carrying out second annealing on the precursor obtained in the step (3) to obtain the Ru-ZnO photocatalyst.
The zinc oxalate is obtained by mixing zinc salt, oxalic acid and water and carrying out precipitation reaction. The mixing operation of the zinc salt, oxalic acid and water is not particularly limited in the invention, and the mixing technical scheme known to those skilled in the art can be adopted. In the present invention, the zinc salt is preferably mixed with oxalic acid and water by dissolving the zinc salt and water completely under stirring, followed by adding oxalic acid. The stirring speed and time are not specially limited, and the components are uniformly mixed.
In the present invention, the mass ratio of the zinc salt to oxalic acid is preferably (1:1) to (1:2), more preferably 1: 2; the mass ratio of the zinc salt to the water is preferably 10g (80-100) mL, and more preferably 10g to 100 mL. In the present invention, the water is capable of dissolving the zinc salt, and the ratio of the mass of the zinc salt to the volume of the water is limited in the above range to ensure more sufficient precipitation reaction.
In the present invention, the zinc salt is preferably zinc nitrate and/or zinc acetate, more preferably zinc acetate dihydrate. In the present invention, the oxalic acid is preferably oxalic acid dihydrate. The sources of the zinc salt and the oxalic acid are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the temperature of the precipitation reaction is preferably room temperature, and more preferably 23-25 ℃. In the invention, the zinc salt is mixed with oxalic acid and water, and the mixture is stirred at room temperature to generate precipitation reaction to obtain the zinc oxalate.
In the invention, the precipitation reaction is preferably carried out under stirring, and the stirring time is preferably 0-60 min, more preferably 20-40 min, and most preferably 30 min. The stirring speed is not specially limited, and the components can be uniformly mixed. In the invention, because the precipitation reaction is accompanied with the formation of the precipitate, the diffusion and mass transfer are slower and slower along with the formation of the precipitate, and the stirring can promote the uniform mixing of the components and the more complete reaction of the reactants.
After the precipitation reaction is completed, the product obtained by the precipitation reaction is preferably washed, dried and ground in sequence to obtain the zinc oxalate. The washing, drying and grinding operations are not particularly limited in the present invention, and washing, drying and grinding schemes known to those skilled in the art can be adopted.
In the present invention, the washing detergent is preferably deionized water or ethanol, and more preferably deionized water. In the present invention, the drying is preferably constant temperature drying; the drying temperature is preferably 40-100 ℃, and more preferably 60-90 ℃; the drying time is preferably 2-5 h. The drying equipment is not particularly limited in the present invention, and a constant temperature drying oven known to those skilled in the art may be used.
In the present invention, the grinding is preferably performed by mortar grinding, and the time for the grinding is not particularly limited, and the zinc oxalate obtained by the precipitation reaction may be dispersed after washing and drying. In the present invention, since the precipitate is washed and dried to cause aggregation, the grinding can disperse the aggregated zinc oxalate.
After obtaining the zinc oxalate, the invention carries out first annealing on the zinc oxalate to obtain ZnO. In the present invention, zinc oxalate is converted into zinc oxide during the first annealing.
In the invention, the temperature of the first annealing is preferably 250-550 ℃, more preferably 300-400 ℃, and most preferably 350 ℃; the time of the first annealing is preferably 1 to 10 hours, more preferably 5 to 7 hours, and most preferably 6 hours. The equipment for the first annealing is not particularly limited in the present invention, and annealing equipment known to those skilled in the art may be used.
After ZnO is obtained, the ZnO, ruthenium chloride and water are mixed for oxidation-reduction reaction to obtain a precursor. The operation of mixing the ZnO, the ruthenium chloride and the water is not particularly limited in the invention, and a mixing technical scheme well known to those skilled in the art can be adopted. In the present invention, the ZnO is preferably mixed with ruthenium chloride and water: the zinc oxide was dispersed uniformly in water with stirring and then ruthenium chloride was added. The stirring speed and time are not specially limited, and the components are uniformly mixed.
In the present invention, the mass ratio of the ruthenium element to the ZnO in the ruthenium chloride is preferably (0.05:100) to (1:100), and more preferably (0.1:100) to (0.5: 100). In the invention, when the mass ratio of the ruthenium element in the ruthenium chloride to the ZnO is in the range, the obtained catalyst has higher efficiency of catalyzing and degrading methane and better stable cyclicity. The source of the ruthenium chloride is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the temperature of the redox reaction is preferably room temperature, and more preferably 23-25 ℃. In the present invention, the redox reaction is preferably performed by stirring and then standing. In the invention, the stirring time is preferably 1-6 h, more preferably 3-4 h, and most preferably 3 h; the standing time is preferably 1-2 h, and more preferably 1 h. In the present invention, the stirring is preferably mechanical stirring. The stirring speed is not specially limited, and the components are uniformly mixed. The stirring device of the present invention is not particularly limited, and a stirring device known to those skilled in the art may be used. In the invention, the stirring and standing are performed firstly to ensure that the reaction system is uniform, promote the reaction between ruthenium in the ruthenium chloride and ZnO, and fully perform the oxidation-reduction reaction.
After the redox reaction is completed, the invention preferably sequentially filters and dries the products of the redox reaction to obtain the precursor. The operation of filtration and drying is not particularly limited in the present invention, and a filtration and drying scheme known to those skilled in the art may be employed. In the present invention, the filtration is preferably suction filtration. In the invention, the drying temperature is preferably 40-70 ℃, and more preferably 50-60 ℃; the drying time is preferably 8-10 h.
After the precursor is obtained, the precursor is subjected to second annealing to obtain the Ru-ZnO photocatalyst. In the invention, the second annealing temperature is preferably 30-350 ℃, more preferably 150-250 ℃, and most preferably 200 ℃; the second annealing time is preferably 0-6 h, and more preferably 0.5 h. In the invention, the second annealing has the function of stabilizing ruthenium on ZnO to obtain the Ru-ZnO photocatalyst with stable structure.
The Ru-ZnO photocatalyst prepared by the preparation method provided by the invention is beneficial to adsorbing methane in air, ZnO can absorb sunlight to generate electron and hole pairs, the electron and the hole are separated and transferred to the surface of a semiconductor, and the electron and the hole transferred to the surface of the semiconductor and CH adsorbed on the surface of ZnO4Oxidation-reduction reaction occurs, so that the photoelectrocatalysis efficiency is improved; the composition of ZnO and Ru forms a heterostructure, so that the Ru-ZnO photocatalyst has good cycling stability.
The invention also provides the Ru-ZnO photocatalyst prepared by the technical scheme, which comprises a ZnO matrix and Ru loaded on the surface of the ZnO matrix.
In the invention, the specific surface area of the Ru-ZnO photocatalyst is preferably 30-55 m2(ii)/g, more preferably 45 to 55m2(ii)/g; the particle size of the Ru-ZnO photocatalyst is preferably 14-100 nm, and more preferably 14-20 nm.
The invention also provides the Ru-ZnO photocatalyst prepared by the preparation method of the technical scheme or the application of the Ru-ZnO photocatalyst in catalyzing and purifying methane in air. In the present invention, the concentration of methane in the air is preferably 1ppb to 10000ppm, more preferably 100ppb to 1000 ppm.
The method for applying the Ru-ZnO catalyst in catalytic purification of methane in air is not particularly limited, and the method well known in the field can be selected. In the invention, the application method of the Ru-ZnO catalyst in catalyzing and purifying methane in air is preferably a catalytic performance test for carrying out photocatalytic degradation on trace methane gas in atmosphere by using the Ru-ZnO catalyst under simulated sunlight.
In the embodiment of the invention, the implementation process of the catalytic performance test for photocatalytic degradation of trace methane gas in the atmosphere by using the Ru-ZnO catalyst under simulated sunlight is as follows: the Ru-ZnO catalyst is paved at the bottom of a quartz reactor, and the reactor is sealed; then injecting methane gas by adopting a valve-type micro-injector, and placing the reactor in a dark place to ensure that the methane gas achieves adsorption-desorption balance on the surface of the photocatalyst; and then, turning on a simulated sunlight light source of a xenon lamp for illumination, sampling every 1 minute, and detecting the concentration of methane in the reactor at any time by using a gas chromatograph.
The Ru-ZnO photocatalyst provided by the invention is applied to catalyzing and purifying methane in air, can efficiently catalyze and degrade low-concentration methane in air under the conditions of simulating sunlight and normal temperature and pressure, shows excellent performance of catalyzing and purifying the low-concentration methane in the air by photocatalysis, and shows good circulation stability.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 10g of zinc acetate dihydrate into 100mL of deionized water, stirring until the zinc acetate dihydrate is completely dissolved, adding 20g of oxalic acid dihydrate into the solution under stirring (wherein the weight ratio of the zinc acetate dihydrate to the oxalic acid dihydrate is 1:2, stirring for 30min to obtain a zinc oxalate precipitate, then carrying out suction filtration on the zinc oxalate precipitate, washing the zinc oxalate with sufficient water, drying the zinc oxalate at 100 ℃ for 5h, grinding the zinc oxalate into powder, and annealing in air at 350 ℃ for 6h to obtain ZnO powder.
1g of the above ZnO powder was ultrasonically dispersed in 75mL of deionized water and stirred until a uniformly dispersed suspension was formed. Then, the prepared ruthenium chloride solution (0.0964mol/L) was added in an amount of 102.69. mu.L (the weight ratio of Ru element to ZnO in the added ruthenium chloride was 0.1: 100). After addition of the ruthenium chloride solution, stirring was carried out for 3h and subsequently standing for 1h, the precipitate obtained was filtered off with suction and dried at 60 ℃ for 10 h. Grinding the dried product into powder, and annealing in air at 200 ℃ for 30min to obtain the 0.1-Ru-ZnO.
Example 2
ZnO was prepared using the method of example 1.
1g of the above ZnO powder was ultrasonically dispersed in 75mL of deionized water and stirred until a uniformly dispersed suspension was formed. Then, the prepared ruthenium chloride solution (0.0964mol/L) was added in an amount of 51.34. mu.L (the weight ratio of Ru element to ZnO in the added ruthenium chloride was 0.05: 100). After addition of the ruthenium chloride solution, stirring was carried out for 3h and subsequently standing for 1h, the precipitate obtained was filtered off with suction and dried at 60 ℃ for 10 h. Grinding the dried product into powder, and annealing in air at 200 ℃ for 30min to obtain the 0.05-Ru-ZnO.
Example 3
ZnO was prepared using the method of example 1.
1g of the above ZnO powder was ultrasonically dispersed in 75mL of deionized water and stirred until a uniformly dispersed suspension was formed. Then, the prepared ruthenium chloride solution (0.0964mol/L) was added in an amount of 205.38. mu.L (the weight ratio of Ru element to ZnO in the added ruthenium chloride was 0.2: 100). After addition of the ruthenium chloride solution, stirring was carried out for 3h and subsequently standing for 1h, the precipitate obtained was filtered off with suction and dried at 60 ℃ for 10 h. Grinding the dried product into powder, and annealing in air at 200 ℃ for 30min to obtain the 0.2-Ru-ZnO.
Example 4
ZnO was prepared using the method of example 1.
1g of the above ZnO powder was ultrasonically dispersed in 75mL of deionized water and stirred until a uniformly dispersed suspension was formed. Then, the prepared ruthenium chloride solution (0.0964mol/L) was added in an amount of 308.07. mu.L (the weight ratio of Ru element to ZnO in the added ruthenium chloride was 0.3: 100). After addition of the ruthenium chloride solution, stirring was carried out for 3h and subsequently standing for 1h, the precipitate obtained was filtered off with suction and dried at 60 ℃ for 10 h. Grinding the dried product into powder, and annealing in air at 200 ℃ for 30min to obtain the 0.3-Ru-ZnO.
Example 5
ZnO was prepared using the method of example 1.
1g of the above ZnO powder was ultrasonically dispersed in 75mL of deionized water and stirred until a uniformly dispersed suspension was formed. Then, the prepared ruthenium chloride solution (0.0964mol/L) was added in an amount of 410.76. mu.L (the weight ratio of Ru element to ZnO in the added ruthenium chloride was 0.4: 100). After addition of the ruthenium chloride solution, stirring was carried out for 3h and subsequently standing for 1h, the precipitate obtained was filtered off with suction and dried at 60 ℃ for 10 h. Grinding the dried product into powder, and annealing in air at 200 ℃ for 30min to obtain the 0.4-Ru-ZnO.
Example 6
ZnO was prepared using the method of example 1.
1g of the above ZnO powder was ultrasonically dispersed in 75mL of deionized water and stirred until a uniformly dispersed suspension was formed. Then, the prepared ruthenium chloride solution (0.0964mol/L) was added in an amount of 513.45. mu.L (the weight ratio of Ru element to ZnO in the added ruthenium chloride was 0.5: 100). After addition of the ruthenium chloride solution, stirring was carried out for 3h and subsequently standing for 1h, the precipitate obtained was filtered off with suction and dried at 60 ℃ for 10 h. Grinding the dried product into powder, and annealing in air at 200 ℃ for 30min to obtain 0.5-Ru-ZnO.
Application examples 1 to 6
1) The Ru-ZnO catalysts (0.05-Ru-ZnO, 0.1-Ru-ZnO, 0.2-Ru-ZnO, 0.3-Ru-ZnO, 0.4-Ru-ZnO and 0.5-Ru-ZnO) prepared in the examples 1-6 are subjected to a catalytic performance test for photocatalytic degradation of trace methane gas in the atmosphere under simulated sunlight:
the implementation process is as follows: respectively weighing 0.3g of the Ru-ZnO catalyst prepared in the examples 1-6, paving the Ru-ZnO catalyst at the bottom of a quartz reactor with the volume of 240mL, and sealing the reactor; then, 24. mu.L of methane gas was injected using a valve-type microinjector so that the concentration of methane in the reactor became 100 ppm. Placing the reactor for 1 hour in a dark place to ensure that methane gas reaches adsorption-desorption balance on the surface of the photocatalyst; and then, turning on a simulated sunlight light source of a 300W xenon lamp for illumination, sampling once every 1 minute, and detecting the concentration of methane in the reactor at any time by using a gas chromatograph.
The test results are shown in FIG. 1, wherein the curves 0.05-Ru, 0.1-Ru, 0.2-Ru, 0.3-Ru, 0.4-Ru and 0.5-Ru represent the catalysts 0.05-Ru-ZnO, 0.1-Ru-ZnO, 0.2-Ru-ZnO, 0.3-Ru-ZnO, 0.4-Ru-ZnO and 0.5-Ru-ZnO prepared in examples 1-6, respectively. As can be seen from the figure, under the simulated sunlight irradiation, for the curve 0.05-Ru, the methane concentration in the reactor is lower than 1% after 5 minutes, and the degradation can be considered to be finished; while the curves 0.1-Ru, 0.2-Ru, 0.3-Ru, 0.4-Ru and 0.5-Ru only need 4 minutes to completely degrade the methane in the reactor, and the photocatalyst in the concentration range shows excellent performance of degrading the methane by photocatalysis. Therefore, 0.1-0.5-Ru-ZnO shows excellent performance of photocatalytic purification of low-concentration methane in air under simulated sunlight, and has strong practical application value.
2) And (3) testing the cycling stability:
the 0.1-Ru-ZnO photocatalyst prepared in example 1 was subjected to ten photocatalytic degradation experiments continuously under the same conditions as described above according to the procedure in application example 1, and the 0.1-Ru-ZnO photocatalyst was used for the next test without any treatment after the test was performed once. The cyclic stability result is shown in fig. 2, and as can be seen from fig. 2, the 0.1-Ru-ZnO photocatalyst shows good stability in ten cyclic degradation tests, and provides good guarantee for the practical application of the photocatalyst.
The embodiment shows that the Ru-ZnO catalyst provided by the invention has high-efficiency catalytic performance and stability on methane under the condition of simulating sunlight, namely, has good photocatalytic activity and stability on the photocatalytic purification of methane at normal temperature and normal pressure.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a Ru-ZnO photocatalyst comprises the following steps:
(1) mixing zinc salt, oxalic acid and water, and carrying out precipitation reaction to obtain zinc oxalate;
(2) performing first annealing on the zinc oxalate obtained in the step (1) to obtain ZnO;
(3) mixing the ZnO obtained in the step (2) with ruthenium chloride and water, and carrying out redox reaction to obtain a precursor;
(4) and (4) carrying out second annealing on the precursor obtained in the step (3) to obtain the Ru-ZnO photocatalyst.
2. The preparation method according to claim 1, wherein the zinc salt in the step (1) is zinc nitrate and/or zinc acetate.
3. The production method according to claim 1, wherein the mass ratio of the zinc salt to the oxalic acid in the step (1) is (1:1) to (1: 2).
4. The method according to claim 1, wherein the temperature of the first annealing in the step (2) is 250 to 550 ℃.
5. The method according to claim 1 or 4, wherein the time for the first annealing in the step (2) is 1 to 10 hours.
6. The production method according to claim 1, wherein the mass ratio of the ruthenium element to the ZnO in the ruthenium chloride in the step (3) is (0.05:100) to (1: 100).
7. The method according to claim 1, wherein the temperature of the second annealing in the step (4) is 30 to 350 ℃.
8. The method according to claim 1 or 7, wherein the time for the second annealing in the step (4) is 0 to 6 hours.
9. The Ru-ZnO photocatalyst prepared by the preparation method of any one of claims 1-8 comprises a ZnO matrix and Ru loaded on the surface of the ZnO matrix.
10. The use of the Ru-ZnO photocatalyst of claim 9 for catalytically purifying methane in air, wherein the concentration of methane in air is 1ppb to 10000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010410522.4A CN111545197B (en) | 2020-05-15 | 2020-05-15 | Application of Ru-ZnO photocatalyst in catalytic purification of methane in air |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010410522.4A CN111545197B (en) | 2020-05-15 | 2020-05-15 | Application of Ru-ZnO photocatalyst in catalytic purification of methane in air |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111545197A true CN111545197A (en) | 2020-08-18 |
| CN111545197B CN111545197B (en) | 2023-02-28 |
Family
ID=71998715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010410522.4A Active CN111545197B (en) | 2020-05-15 | 2020-05-15 | Application of Ru-ZnO photocatalyst in catalytic purification of methane in air |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111545197B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113117670A (en) * | 2021-04-22 | 2021-07-16 | 湖北大学 | Mn-ZnO catalyst and preparation method and application thereof |
| CN113578319A (en) * | 2021-07-30 | 2021-11-02 | 陕西瑞科新材料股份有限公司 | Preparation method of zinc oxide-based platinum particle catalyst |
| CN114965651A (en) * | 2022-05-19 | 2022-08-30 | 湖北大学 | ZnO-based methane sensor and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020131925A1 (en) * | 2000-09-25 | 2002-09-19 | Engelhard Corporation | Ruthenium oxidation catalyst |
| CN106622227A (en) * | 2016-12-29 | 2017-05-10 | 天津大学 | Preparation method of monoatomic catalyst for indoor air purification |
| CN107051433A (en) * | 2017-03-08 | 2017-08-18 | 华东理工大学 | The preparation method of zinc oxide supported palladium/platinum catalyst and the application in CO catalysis oxidations |
| CN108855076A (en) * | 2018-06-05 | 2018-11-23 | 山东大学 | A kind of Ag/ZnO composite photo-catalyst and its preparation method and application |
| CN110833834A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of supported ruthenium-copper bimetallic catalyst, product and application thereof |
-
2020
- 2020-05-15 CN CN202010410522.4A patent/CN111545197B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020131925A1 (en) * | 2000-09-25 | 2002-09-19 | Engelhard Corporation | Ruthenium oxidation catalyst |
| CN106622227A (en) * | 2016-12-29 | 2017-05-10 | 天津大学 | Preparation method of monoatomic catalyst for indoor air purification |
| CN107051433A (en) * | 2017-03-08 | 2017-08-18 | 华东理工大学 | The preparation method of zinc oxide supported palladium/platinum catalyst and the application in CO catalysis oxidations |
| CN108855076A (en) * | 2018-06-05 | 2018-11-23 | 山东大学 | A kind of Ag/ZnO composite photo-catalyst and its preparation method and application |
| CN110833834A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of supported ruthenium-copper bimetallic catalyst, product and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| J. Z. BLOH,ET AL.: "《Transition metal-modified zinc oxides for UV and visible light photocatalysis》", 《ENVIRON SCI POLLUT RES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113117670A (en) * | 2021-04-22 | 2021-07-16 | 湖北大学 | Mn-ZnO catalyst and preparation method and application thereof |
| CN113578319A (en) * | 2021-07-30 | 2021-11-02 | 陕西瑞科新材料股份有限公司 | Preparation method of zinc oxide-based platinum particle catalyst |
| CN113578319B (en) * | 2021-07-30 | 2023-10-03 | 陕西瑞科新材料股份有限公司 | Preparation method of zinc oxide-based platinum particle catalyst |
| CN114965651A (en) * | 2022-05-19 | 2022-08-30 | 湖北大学 | ZnO-based methane sensor and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111545197B (en) | 2023-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111545197B (en) | Application of Ru-ZnO photocatalyst in catalytic purification of methane in air | |
| CN107824210B (en) | Titanium dioxide composite photocatalyst coated by nitrogen-doped mesoporous carbon and preparation method and application thereof | |
| CN108706573B (en) | graphene-based hollow cobalt sulfide nanocrystalline capable of efficiently activating persulfate and preparation method thereof | |
| CN111036285B (en) | Photocatalyst of nitrogen modified perovskite composite molecular sieve and preparation method and application method thereof | |
| CN106975481B (en) | The preparation method of alkaline earth metal doping MnO2 catalyst with efficient photo-thermal concerted catalysis purifying VOCs | |
| CN111167478B (en) | CdS-Bi 2 WO 6 Application of semiconductor Z-type heterojunction in photocatalytic degradation of ethylene | |
| CN105749893A (en) | Preparation method of modified active carbon fiber with surface-loaded nanometer titanium dioxide (TiO2) | |
| CN110694691A (en) | photo-Fenton catalyst, preparation method and application method | |
| CN106064101A (en) | A kind of iron-based MOFs catalysis material and preparation and application thereof | |
| CN102861597B (en) | Catalyst capable of responding to visible light and being used for producing hydrogen by photocatalytic water splitting and preparation method of catalyst | |
| CN104772138B (en) | MnOx/graphene low-temperature SCR flue gas denitration catalyst, preparation method and applications thereof | |
| CN112547045A (en) | Preparation method of photocatalytic denitration catalyst with porous titanium dioxide as carrier | |
| CN114409898B (en) | Amino-modified covalent triazinyl skeleton and preparation method and application thereof | |
| CN109158117B (en) | Full-spectrum-response double-doped lanthanum fluoride/attapulgite up-conversion composite photocatalytic material and preparation method and application thereof | |
| CN103342402A (en) | Method for degrading methylene blue by using nitrogen-doped oxygen vacancy type TiO2 catalyst | |
| CN111408361A (en) | Formaldehyde degradation material based on waste lead-zinc ore tailings and preparation method thereof | |
| CN113145108A (en) | MnO capable of adjusting oxygen species distributionxCatalyst, preparation method and application thereof | |
| CN111111641B (en) | Cerium dioxide-based catalyst and preparation method and application thereof | |
| CN108816211B (en) | Preparation method of blue rutile titanium dioxide ceramic material with high catalytic activity | |
| CN111686777A (en) | NiS-g-C3N4Method for preparing photocatalyst | |
| CN113117670A (en) | Mn-ZnO catalyst and preparation method and application thereof | |
| CN114870879A (en) | Bimetal perovskite load graphene-like carbon nitride visible-light-induced photocatalyst and preparation method thereof | |
| CN108889320B (en) | Oxygen vacancy type ternary halide photocatalyst and preparation method and application thereof | |
| CN108465464B (en) | Preparation method and application of barium strontium titanate/bismuth vanadate | |
| CN113797910A (en) | Defect-containing nano microspheric perovskite catalyst and preparation method and application thereof |
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 |