CN109482200B - Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof - Google Patents
Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109482200B CN109482200B CN201811382910.5A CN201811382910A CN109482200B CN 109482200 B CN109482200 B CN 109482200B CN 201811382910 A CN201811382910 A CN 201811382910A CN 109482200 B CN109482200 B CN 109482200B
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- molybdenum sulfide
- carbon supported
- supported
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 110
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000004321 preservation Methods 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960001553 phloroglucinol Drugs 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 10
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 5
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 230000002950 deficient Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 7
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 12
- 239000002135 nanosheet Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 229910052961 molybdenite Inorganic materials 0.000 description 11
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000000527 sonication Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 125000002444 phloroglucinyl group Chemical group [H]OC1=C([H])C(O[H])=C(*)C(O[H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- B01J35/60—
Abstract
The invention belongs to the field of catalysis and energy storage materials, and discloses a porous carbon supported defected molybdenum sulfide electrocatalyst and a preparation method thereof. Reacting monosaccharide, phloroglucinol and graphene oxide in an alcohol-water mixed solvent, freeze-drying a product, carbonizing at 700-900 ℃, and heating and dipping with concentrated nitric acid to obtain functionalized porous carbon; heating ammonium molybdate, thiourea and functionalized porous carbon in water to 180-240 ℃ for heat preservation reaction to obtain porous carbon supported molybdenum sulfide; mixing the porous carbon supported molybdenum sulfide with red phosphorus, and then carbonizing at 600-900 ℃ in the mixed atmosphere of hydrogen and argon to obtain the porous carbon supported defected molybdenum sulfide electrocatalyst. The raw materials used in the preparation method are cheap and easily available, and MoS in the obtained product2The nanosheets are petal-shaped and vertically grow on the porous carbon substrate, have more edge active sites and are high in catalytic activity.
Description
Technical Field
The invention belongs to the field of catalysis and energy storage materials, and particularly relates to a porous carbon supported defected molybdenum sulfide electrocatalyst and a preparation method thereof.
Background
The development of industry and the improvement of human living standard can not keep away from the consumption of energy. The consumption of traditional energy sources generates more carbon oxides, nitrogen oxides, acid rain and the like, thus causing serious pollution to the environment. In order to solve the problems of energy crisis, environmental pollution and the like, development and utilization of environment-friendly, clean, low-cost and renewable energy systems have gradually attracted extensive attention. The oxygen reduction reaction and the hydrogen evolution reaction play a key role in the fields of fuel cells, zinc-air cells, anticorrosion protection and the like. To date, noble metal-based catalysts, including Pt, Pd, Ru and their alloys, have been widely used as ORR and HER reactions due to their low initial potential and small tafel slope. However, it has disadvantages of high cost, low storage capacity, and low toxicity resistance, which prevents the wide use of noble metal catalysts. Therefore, the development of non-noble metal-based electrocatalysts with high activity, good stability and low cost is urgently needed for the development of hydrogen production by water electrolysis.
Currently, there has been a great deal of research effort focused on developing non-noble metal-based catalysts that exhibit good electrocatalytic properties for HER or ORR, with the transition metal-based catalysts being widely and mature studied, mainly phosphides, carbides, selenides, nitrides and sulfides. MoS2Due to unique electronic, chemical and physical properties, the electrolyte is widely used in the fields of super capacitors, lithium ion batteries, hydrogen production by water electrolysis and the like. MoS, a typical transition metal chalcogenide2Is composed of three stacked atomic layers (S-Mo-S) that are connected together by van der waals forces. The single-layer molybdenum disulfide is a sandwich structure similar to a sandwich, the upper layer and the lower layer are sulfur atoms, and the layer added in the middle of the two layers is molybdenum atoms. Each layer having a thickness of about 0.7nm and a layer-to-layer spacing of
MoS2The crystal structure of (A) mainly comprises 1T-MoS2(Square symmetrical), 2H-MoS2(Hexagon symmetry) and 3R-MoS2(orthorhombic hexagonal symmetry). The results of experiments and calculations show that MoS2The hydrogen evolution catalytically active sites of (a) are mainly derived from the sulfur edge, whereas the basal plane is inert. In addition, nano-sized MoS due to the presence of more exposed active sites2Should be more active than the body type. Therefore, MoS with more edge sites was designed2Is to improve MoS2One of the possible strategies for base electrocatalyst activity. High electrical conductivity canSo as to ensure the rapid transfer of electrons in the catalysis process, and is important for the catalytic activity of the catalyst. MoS2The relatively large band gap, which exhibits poor conductivity, significantly limits the rate of the hydrogen evolution reaction.
Carbonaceous materials, such as carbon nanotubes, carbon fibers, porous carbon, carbon spheres, carbon nanosheets and graphene, can be directly used as a catalyst for hydrogen production by water electrolysis and also widely applied to the preparation of excellent carriers of hybrid catalysts due to the advantages of high electronic conductivity, low density, low cost, easiness in synthesizing porous structures and the like. It can be compounded with other noble metals or cheap metals to form high-catalytic-activity catalyst. Although and MoS2Composite carbonaceous materials have been developed and applied for electrochemical catalysis, but at the same time exposing more active sites and improving stability remains an important challenge.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a porous carbon supported defected molybdenum sulfide electrocatalyst.
Another object of the present invention is to provide a porous carbon supported defected molybdenum sulfide electrocatalyst prepared by the above method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a porous carbon supported defected molybdenum sulfide electrocatalyst comprises the following preparation steps:
(1) preparation of functionalized porous carbon: under magnetic stirring, dissolving monosaccharide and phloroglucinol in a mixed solvent consisting of alcohol and water, adding Graphene Oxide (GO) for ultrasonic dispersion, heating to 150-200 ℃ for heat preservation reaction, washing and freeze-drying a solid product, then carrying out carbonization treatment in an inert atmosphere at the temperature of 700-900 ℃, and heating and dipping the obtained product by concentrated nitric acid to obtain functionalized porous carbon;
(2) preparing porous carbon supported molybdenum sulfide: dissolving ammonium molybdate and thiourea in water, adding the functionalized porous carbon obtained in the step (1), performing ultrasonic treatment to form uniform suspension, heating to 180-240 ℃, and performing heat preservation reaction to obtain porous carbon-supported molybdenum sulfide;
(3) preparation of porous carbon supported defective molybdenum sulfide: mixing molybdenum sulfide carried by porous carbon with red phosphorus, and then mixing the mixture in hydrogen and argon (Ar/H)2) Carbonizing at 600-900 ℃ in the atmosphere to obtain the porous carbon supported defected molybdenum sulfide electrocatalyst.
Preferably, the monosaccharide in step (1) refers to one or a mixture of more than two of D-xylose, glucose and fructose.
Preferably, the mass ratio of the monosaccharide to the phloroglucinol added in the step (1) is (1-3): 1.
Preferably, in the mixed solvent composed of alcohol and water in the step (1), the volume ratio of alcohol to water is 1 (1-3).
Preferably, the time of the heat preservation reaction in the step (1) is 12-24 hours, and the time of the carbonization treatment is 2-5 hours.
Preferably, the temperature of the concentrated nitric acid heating and dipping treatment in the step (1) is 90-120 ℃, and the time is 1-3 hours.
Preferably, the ratio of the amount of the substances added into the ammonium molybdate and the thiourea in the step (2) is (0.1-0.5): (1-10).
Preferably, the time of the heat preservation reaction in the step (2) is 20-24 h.
Preferably, the mass ratio of the porous carbon-supported molybdenum sulfide to the red phosphorus in the step (3) is 1 (1-10).
Preferably, the carbonization treatment time in the step (3) is 1-5 h.
A porous carbon supported defected molybdenum sulfide electrocatalyst is prepared by the method.
The preparation principle of the invention is as follows:
under the hydrothermal condition, graphene oxide, monosaccharide and phloroglucinol form hydrogel in a self-assembly mode, and the porous carbon material is obtained through freeze drying and carbonization treatment. The porous carbon surface is rich in oxygen-containing functional groups through the acidification treatment of concentrated nitric acid, so that the hydrophilicity and hydrophobicity of the interface of the porous carbon are changed. Subsequently, a hybrid of molybdenum sulfide and porous carbon was prepared by means of hydrothermal synthesis. Finally, red phosphorus is introduced into a hybrid of molybdenum sulfide and porous carbon, and in the high-temperature reduction process, phosphorus atoms replace sulfur atoms in the molybdenum sulfide, so that the molybdenum sulfide is defected.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) the invention utilizes the self-assembly of cheap and easily-obtained monosaccharide and phloroglucinol to prepare a biomass-based carbon material used as a conductive carrier, and then prepares the monosaccharide-based porous carbon-supported defected molybdenum sulfide electrocatalyst by a one-step hydrothermal method and a carbothermic reduction method. On the basis of reasonably utilizing biomass resources, a new idea is provided for the development of subsequent electrocatalysts.
(2) The molybdenum sulfide nanosheets in the product obtained by the method are vertically arranged and grown on the monosaccharide-based porous carbon carrier, so that more edge active sites are exposed, the catalytic activity of the catalyst is promoted to be improved, and the defect at the later stage is realized.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the functionalized porous carbon (a, b) obtained in step (1) and the porous carbon supporting molybdenum sulfide (c, d) obtained in step (2) of example 5.
Fig. 2 is an X-ray diffraction (XRD) spectrum of the molybdenum sulfide supported by the porous carbon obtained in step (2) and the defected molybdenum sulfide supported by the porous carbon obtained in step (3) of example 5.
FIG. 3 is a polarization diagram of hydrogen production from electrolysis of water with 0.5M sulfuric acid using a porous carbon supported defected molybdenum sulfide (1:10) prepared in example 5 and a conventional palladium-carbon catalyst (20% Pt/C).
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The preparation method of the porous carbon supported defected molybdenum sulfide electrocatalyst provided by the embodiment comprises the following specific preparation steps:
(1) preparation of functionalized porous carbon: 0.1g D-xylose and 0.1g phloroglucinol were dissolved in 10mL of a mixed solution composed of alcohol and water (alcohol-water volume ratio 1:2) under magnetic stirring. Next, 5mL of 1mmol/L GO was slowly added to the solution and uniformly dispersed by sonication for 0.5 h. Subsequently, the mixture solution was transferred to a 50mL autoclave with a polytetrafluoroethylene substrate and heated to 180 ℃ for 16 hours. The solid product is washed with water and lyophilized to obtain the porous carbon material. The porous carbon was heated in a 700 ℃ tube furnace for 2h under nitrogen atmosphere. And then further heating and dipping the carbonized porous carbon for 1h by using concentrated nitric acid at 90 ℃, wherein the obtained product is functionalized porous carbon.
(2) Preparing porous carbon supported molybdenum sulfide: dissolving 0.2mmol of ammonium molybdate and 1mmol of thiourea in 35mL of water, stirring uniformly, adding 0.05g of functionalized porous carbon into the solution, and carrying out ultrasonic treatment for 30min to form uniform suspension. And transferring the suspension into a 50mL autoclave with a polytetrafluoroethylene substrate, heating to 200 ℃, and carrying out heat preservation reaction for 24 hours to obtain the porous carbon supported molybdenum sulfide.
(3) Preparation of porous carbon supported defective molybdenum sulfide: grinding and mixing a porous carbon-supported molybdenum sulfide material and red phosphorus (in a mass ratio of 1:1), and mixing the mixture in Ar/H2Carbonizing for 1h at 600 ℃ in the atmosphere to obtain the porous carbon supported defected molybdenum sulfide electrocatalyst.
Example 2
The preparation method of the porous carbon supported defected molybdenum sulfide electrocatalyst provided by the embodiment comprises the following specific preparation steps:
(1) preparation of functionalized porous carbon: 0.5g D-xylose and 0.2g phloroglucinol were dissolved in 10mL of a mixed solution composed of alcohol and water (alcohol-water volume ratio 1:1) under magnetic stirring. Next, 5mL of 1mmol/L GO was slowly added to the solution and uniformly dispersed by sonication for 0.5 h. Subsequently, the mixture solution was transferred to a 50mL autoclave with a polytetrafluoroethylene substrate and heated to 180 ℃ for 16 hours. The solid product is washed with water and lyophilized to obtain the porous carbon material. The porous carbon was heated in a 800 ℃ tube furnace for 2h under nitrogen atmosphere. And then further heating and dipping the carbonized porous carbon for 1h by using concentrated nitric acid at 90 ℃, wherein the obtained product is functionalized porous carbon.
(2) Preparing porous carbon supported molybdenum sulfide: 0.5mmol of ammonium molybdate and 1mmol of thiourea are dissolved in 35mL of water and stirred uniformly, 0.05g of functionalized porous carbon is added into the solution, and ultrasonic treatment is carried out for 30min to form uniform suspension. And transferring the suspension into a 50mL autoclave with a polytetrafluoroethylene substrate, heating to 200 ℃, and carrying out heat preservation reaction for 24 hours to obtain the porous carbon supported molybdenum sulfide.
(3) Preparation of porous carbon supported defective molybdenum sulfide: grinding and mixing a porous carbon-supported molybdenum sulfide material and red phosphorus (in a mass ratio of 1:1), and mixing the mixture in Ar/H2Carbonizing for 1h at 700 ℃ in the atmosphere to obtain the porous carbon supported defected molybdenum sulfide electrocatalyst.
Example 3
The preparation method of the porous carbon supported defected molybdenum sulfide electrocatalyst provided by the embodiment comprises the following specific preparation steps:
(1) preparation of functionalized porous carbon: 0.89g D-xylose and 0.31g phloroglucinol were dissolved in 10mL of a mixed solution composed of alcohol and water (alcohol-water volume ratio of 1:3) under magnetic stirring. Next, 5mL of 1mmol/L GO was slowly added to the solution and uniformly dispersed by sonication for 0.5 h. Subsequently, the mixture solution was transferred to a 50mL autoclave with a polytetrafluoroethylene substrate and heated to 180 ℃ for 16 hours. The solid product is washed with water and lyophilized to obtain the porous carbon material. The porous carbon was heated in a 800 ℃ tube furnace for 2h under nitrogen atmosphere. And then further heating and dipping the carbonized porous carbon for 1h by using concentrated nitric acid at 90 ℃, wherein the obtained product is functionalized porous carbon.
(2) Preparing porous carbon supported molybdenum sulfide: dissolving 0.2mmol of ammonium molybdate and 6mmol of thiourea in 35mL of water, stirring uniformly, adding 0.05g of functionalized porous carbon into the solution, and carrying out ultrasonic treatment for 30min to form uniform suspension. And transferring the suspension into a 50mL autoclave with a polytetrafluoroethylene substrate, heating to 200 ℃, and carrying out heat preservation reaction for 24 hours to obtain the porous carbon supported molybdenum sulfide.
(3) Preparation of porous carbon supported defective molybdenum sulfide: grinding and mixing a porous carbon-supported molybdenum sulfide material and red phosphorus (in a mass ratio of 1:1), and mixing the mixture in Ar/H2Carbonizing at 750 deg.C for 1h in atmosphere to obtainA porous carbon supported defected molybdenum sulfide electrocatalyst is provided.
Example 4
The preparation method of the porous carbon supported defected molybdenum sulfide electrocatalyst provided by the embodiment comprises the following specific preparation steps:
(1) preparation of functionalized porous carbon: 0.89g D-xylose and 0.31g phloroglucinol were dissolved in 10mL of a mixed solution composed of alcohol and water (alcohol-water volume ratio 1:2) under magnetic stirring. Next, 5mL of 1mmol/L GO was slowly added to the solution and uniformly dispersed by sonication for 0.5 h. Subsequently, the mixture solution was transferred to a 50mL autoclave with a polytetrafluoroethylene substrate and heated to 180 ℃ for 16 hours. The solid product is washed with water and lyophilized to obtain the porous carbon material. The porous carbon was heated in a 800 ℃ tube furnace for 2h under nitrogen atmosphere. And then further heating and dipping the carbonized porous carbon for 1h by using concentrated nitric acid at 90 ℃, wherein the obtained product is functionalized porous carbon.
(2) Preparing porous carbon supported molybdenum sulfide: dissolving 0.2mmol of ammonium molybdate and 6mmol of thiourea in 35mL of water, stirring uniformly, adding 0.05g of functionalized porous carbon into the solution, and carrying out ultrasonic treatment for 30min to form uniform suspension. And transferring the suspension into a 50mL autoclave with a polytetrafluoroethylene substrate, heating to 200 ℃, and carrying out heat preservation reaction for 24 hours to obtain the porous carbon supported molybdenum sulfide.
(3) Preparation of porous carbon supported defective molybdenum sulfide: grinding and mixing a porous carbon-supported molybdenum sulfide material and red phosphorus (in a mass ratio of 1:5), and mixing the mixture in Ar/H2Carbonizing for 1h at 750 ℃ in the atmosphere to obtain the porous carbon supported defected molybdenum sulfide electrocatalyst.
Example 5
The preparation method of the porous carbon supported defected molybdenum sulfide electrocatalyst provided by the embodiment comprises the following specific preparation steps:
(1) preparation of functionalized porous carbon: 0.89g D-xylose and 0.31g phloroglucinol were dissolved in 10mL of a mixed solution composed of alcohol and water (alcohol-water volume ratio 1:2) under magnetic stirring. Next, 5mL of 1mmol/L GO was slowly added to the solution and uniformly dispersed by sonication for 0.5 h. Subsequently, the mixture solution was transferred to a 50mL autoclave with a polytetrafluoroethylene substrate and heated to 180 ℃ for 16 hours. The solid product is washed with water and lyophilized to obtain the porous carbon material. The porous carbon was heated in a 800 ℃ tube furnace for 2h under nitrogen atmosphere. And then further heating and dipping the carbonized porous carbon for 1h by using concentrated nitric acid at 90 ℃, wherein the obtained product is functionalized porous carbon.
(2) Preparing porous carbon supported molybdenum sulfide: dissolving 0.2mmol of ammonium molybdate and 6mmol of thiourea in 35mL of water, stirring uniformly, adding 0.05g of functionalized porous carbon into the solution, and carrying out ultrasonic treatment for 30min to form uniform suspension. And transferring the suspension into a 50mL autoclave with a polytetrafluoroethylene substrate, heating to 200 ℃, and carrying out heat preservation reaction for 24 hours to obtain the porous carbon supported molybdenum sulfide.
(3) Preparation of porous carbon supported defective molybdenum sulfide: grinding and mixing a porous carbon-supported molybdenum sulfide material and red phosphorus (in a mass ratio of 1:10), and mixing the mixture in Ar/H2Carbonizing for 1h at 750 ℃ in the atmosphere to obtain the porous carbon supported defected molybdenum sulfide electrocatalyst.
Fig. 1 shows Scanning Electron Microscope (SEM) images of the functionalized porous carbon (a, b) obtained in step (1) and the porous carbon supporting molybdenum sulfide (c, d) obtained in step (2) in this example. As can be seen from fig. 1 a and b, the material after freeze-drying exhibits a three-dimensional porous structure, which comprises a part of a sheet-like bulk structure. In FIG. 1 c and d indicate MoS2The nano-sheets are petal-shaped and vertically grow on the porous carbon substrate, and the agglomeration phenomenon is hardly generated. Upon continued magnification of the SEM of the hybrid material, MoS can be observed2The surface of the nano sheet is smooth, and the thickness of the nano sheet is about 10-40 nm.
The X-ray diffraction (XRD) patterns of the molybdenum sulfide supported by the porous carbon obtained in step (2) and the defective molybdenum sulfide supported by the porous carbon obtained in step (3) of this example are shown in fig. 2. From the XRD pattern of the molybdenum sulfide supported on porous carbon, it can be seen that peaks at 13.77, 33.38, 39.32 and 58.93 ° correspond to the hexagonal MoS2The (002), (100), (103) and (110) crystal planes (JCPDS # 73-1508). For the spectrum of the porous carbon supported defected molybdenum sulfide, peaks at 27.77, 32.04, 42.90, 57.18, 64.77, 67.27, 74.04 and 85.44 degrees 2 theta can be assigned to MoPThe (001), (100), (101), (110), (111), (200), (201) and (112) crystal planes of the phases (JCPDS # 24-0771).
The polarization curves of the porous carbon supported defected molybdenum sulfide (1:10) prepared in the example and the conventional palladium carbon catalyst (20% Pt/C) in the hydrogen production by water electrolysis of 0.5M sulfuric acid are shown in FIG. 3. As can be seen from figure 3, the hydrogen production by electrolyzing water of the porous carbon supported defective molybdenum sulfide prepared by the invention has the current density of 10mA/cm2The overpotential at (c) was 144 mV.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a porous carbon supported defected molybdenum sulfide electrocatalyst is characterized by comprising the following preparation steps:
(1) preparation of functionalized porous carbon: under magnetic stirring, dissolving monosaccharide and phloroglucinol in a mixed solvent consisting of alcohol and water, adding graphene oxide, performing ultrasonic dispersion uniformly, heating to 150-200 ℃, performing heat preservation reaction, washing and freeze-drying a solid product, performing carbonization treatment in an inert atmosphere at 700-900 ℃, and heating and dipping the obtained product by concentrated nitric acid to obtain functionalized porous carbon;
(2) preparing porous carbon supported molybdenum sulfide: dissolving ammonium molybdate and thiourea in water, adding the functionalized porous carbon obtained in the step (1), performing ultrasonic treatment to form uniform suspension, heating to 180-240 ℃, and performing heat preservation reaction to obtain porous carbon-supported molybdenum sulfide;
(3) preparation of porous carbon supported defective molybdenum sulfide: mixing the porous carbon supported molybdenum sulfide with red phosphorus, and then carbonizing at 600-900 ℃ in the mixed atmosphere of hydrogen and argon to obtain the porous carbon supported defected molybdenum sulfide electrocatalyst.
2. The method of preparing a porous carbon supported deficient molybdenum sulfide electrocatalyst according to claim 1, wherein: the monosaccharide in the step (1) refers to one or a mixture of more than two of D-xylose, glucose and fructose.
3. The method of preparing a porous carbon supported deficient molybdenum sulfide electrocatalyst according to claim 1, wherein: the mass ratio of the monosaccharide to the phloroglucinol added in the step (1) is (1-3) to 1.
4. The method of preparing a porous carbon supported deficient molybdenum sulfide electrocatalyst according to claim 1, wherein: in the mixed solvent composed of the alcohol and the water in the step (1), the volume ratio of the alcohol to the water is 1 (1-3).
5. The method of preparing a porous carbon supported deficient molybdenum sulfide electrocatalyst according to claim 1, wherein: in the step (1), the time of the heat preservation reaction is 12-24 hours, and the time of the carbonization treatment is 2-5 hours.
6. The method of preparing a porous carbon supported deficient molybdenum sulfide electrocatalyst according to claim 1, wherein: the temperature of the concentrated nitric acid heating and dipping treatment in the step (1) is 90-120 ℃, and the time is 1-3 h.
7. The method of preparing a porous carbon supported deficient molybdenum sulfide electrocatalyst according to claim 1, wherein: in the step (2), the ratio of the amount of the substances added into the ammonium molybdate and the thiourea is (0.1-0.5) to (1-10).
8. The method of preparing a porous carbon supported deficient molybdenum sulfide electrocatalyst according to claim 1, wherein: and (3) keeping the temperature for 20-24 h.
9. The method of preparing a porous carbon supported deficient molybdenum sulfide electrocatalyst according to claim 1, wherein: in the step (3), the mass ratio of the mixture of the porous carbon-supported molybdenum sulfide and red phosphorus is 1 (1-10); the carbonization treatment time is 1-5 h.
10. A porous carbon supported defected molybdenum sulfide electrocatalyst, characterized by: prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811382910.5A CN109482200B (en) | 2018-11-20 | 2018-11-20 | Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811382910.5A CN109482200B (en) | 2018-11-20 | 2018-11-20 | Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109482200A CN109482200A (en) | 2019-03-19 |
| CN109482200B true CN109482200B (en) | 2021-03-30 |
Family
ID=65697035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811382910.5A Active CN109482200B (en) | 2018-11-20 | 2018-11-20 | Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109482200B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111905767B (en) * | 2020-07-29 | 2021-11-26 | 华南农业大学 | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof |
| CN114790001B (en) * | 2022-05-06 | 2023-10-03 | 河南农业大学 | Polyacid functionalized nitrogen-rich porous carbon and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101658796A (en) * | 2009-09-17 | 2010-03-03 | 南开大学 | New method for preparing molybdenum phosphide by reducing molybdenum trioxide precursor |
| KR20120098354A (en) * | 2011-02-28 | 2012-09-05 | 고려대학교 산학협력단 | Multicomponent non-pt electrode catalysts and fuel cell including electrode comprising the electrode catalysts |
| CN105126876A (en) * | 2015-09-07 | 2015-12-09 | 复旦大学 | Flowerlike carbon-loaded MoS<2> nano-particle composite and preparation method thereof |
| CN105513832A (en) * | 2015-12-16 | 2016-04-20 | 华南理工大学 | Graphene/porous carbon composite hydrogel, graphene/porous carbon composite aerogel, and preparation methods and applications thereof |
| CN105692580A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | Porous carbon material and preparation and application thereof |
| CN107298442A (en) * | 2017-07-15 | 2017-10-27 | 中国海洋大学 | A kind of biomass carbon/molybdenum disulfide nano-composite material and preparation method thereof |
| CN107768663A (en) * | 2017-09-28 | 2018-03-06 | 芜湖恒尼动力电池材料科技有限公司 | The method for preparing the transition metal oxide with oxygen defect |
| CN108217648A (en) * | 2018-01-29 | 2018-06-29 | 山东省圣泉生物质石墨烯研究院 | A kind of compound porous Carbon Materials and preparation method and application |
| CN108452817A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院化学研究所 | A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen |
| CN108767209A (en) * | 2018-04-26 | 2018-11-06 | 昆明理工大学 | A kind of preparation method of phosphorus/porous carbon/graphene composite material |
-
2018
- 2018-11-20 CN CN201811382910.5A patent/CN109482200B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101658796A (en) * | 2009-09-17 | 2010-03-03 | 南开大学 | New method for preparing molybdenum phosphide by reducing molybdenum trioxide precursor |
| KR20120098354A (en) * | 2011-02-28 | 2012-09-05 | 고려대학교 산학협력단 | Multicomponent non-pt electrode catalysts and fuel cell including electrode comprising the electrode catalysts |
| CN105692580A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | Porous carbon material and preparation and application thereof |
| CN105126876A (en) * | 2015-09-07 | 2015-12-09 | 复旦大学 | Flowerlike carbon-loaded MoS<2> nano-particle composite and preparation method thereof |
| CN105513832A (en) * | 2015-12-16 | 2016-04-20 | 华南理工大学 | Graphene/porous carbon composite hydrogel, graphene/porous carbon composite aerogel, and preparation methods and applications thereof |
| CN108452817A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院化学研究所 | A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen |
| CN107298442A (en) * | 2017-07-15 | 2017-10-27 | 中国海洋大学 | A kind of biomass carbon/molybdenum disulfide nano-composite material and preparation method thereof |
| CN107768663A (en) * | 2017-09-28 | 2018-03-06 | 芜湖恒尼动力电池材料科技有限公司 | The method for preparing the transition metal oxide with oxygen defect |
| CN108217648A (en) * | 2018-01-29 | 2018-06-29 | 山东省圣泉生物质石墨烯研究院 | A kind of compound porous Carbon Materials and preparation method and application |
| CN108767209A (en) * | 2018-04-26 | 2018-11-06 | 昆明理工大学 | A kind of preparation method of phosphorus/porous carbon/graphene composite material |
Non-Patent Citations (2)
| Title |
|---|
| "Heterointerface engineering of trilayer-shelled ultrathin MoS2/MoP/N-doped carbon hollow nanobubbles for efficient hydrogen evolution";Jing-Qi Chi et al.;《Journal of Materials Chemistry A》;20181114;第6卷;第24783-24792页 * |
| "MoS2–MoP heterostructured nanosheets on polymer-derived carbon as an electrocatalyst for hydrogen evolution reaction";Zexing Wu et al.;《Journal of Materials Chemistry A》;20171130;第6卷;第616-622页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109482200A (en) | 2019-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ding et al. | Mesoporous nickel-sulfide/nickel/N-doped carbon as HER and OER bifunctional electrocatalyst for water electrolysis | |
| Wen et al. | Well-dispersed Co3Fe7 alloy nanoparticles wrapped in N-doped defect-rich carbon nanosheets as a highly efficient and methanol-resistant catalyst for oxygen-reduction reaction | |
| CN109847778B (en) | Cobalt disulfide/carbon nitrogen composite material for oxygen evolution by electrolyzing water and synthetic method thereof | |
| Wang et al. | Construction of unique ternary composite MCNTs@ CoSx@ MoS2 with three-dimensional lamellar heterostructure as high-performance bifunctional electrocatalysts for hydrogen evolution and oxygen evolution reactions | |
| Hao et al. | Microporous Fe–N4 cataysts derived from biomass aerogel for a high-performance Zn–air battery | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN113881965B (en) | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof | |
| Huang et al. | Ni activated Mo2C nanoparticles supported on stereotaxically-constructed graphene for efficient overall water splitting | |
| CN113644283B (en) | Preparation method of non-metal doped carbon/ferrous sulfide compound | |
| CN111921551A (en) | Preparation method of nitrogen-doped carbon frame material coated with iron-cobalt-nickel ternary alloy | |
| Li et al. | Porous N, P co-doped carbon-coated ultrafine Co2P nanoparticles derived from DNA: an electrocatalyst for highly efficient hydrogen evolution reaction | |
| Miao et al. | A bio-inspired N-doped porous carbon electrocatalyst with hierarchical superstructure for efficient oxygen reduction reaction | |
| CN109482200B (en) | Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof | |
| Cao et al. | Biomass-derived carbon material as efficient electrocatalysts for the oxygen reduction reaction | |
| Ma et al. | Lignin-derived hierarchical porous flower-like carbon nanosheets decorated with biomass carbon quantum dots for efficient oxygen reduction | |
| Deng et al. | Boosting the activity and stability via synergistic catalysis of Co nanoparticles and MoC to construct a bifunctional electrocatalyst for high-performance and long-life rechargeable zinc–air batteries | |
| Xiong et al. | Bionic structural design and electrochemical manufacture of WC/N-doped carbon hybrids as efficient ORR catalyst | |
| CN112909271A (en) | Integral transition metal phosphide electrocatalyst with sea urchin-shaped morphology and preparation method and application thereof | |
| CN111151281B (en) | C 3 N 4 Modified Co 3 O 4 Self-supported ultrathin porous nanosheet and preparation method and application thereof | |
| Han et al. | An assembly of carbon dots and carbon sheets from plant biomass for excellent oxygen reduction reaction | |
| Xu et al. | Lattice defective and N, S co-doped carbon nanotubes for trifunctional electrocatalyst application | |
| CN115954493A (en) | Method for improving activity and stability of supported platinum-based catalyst | |
| Zeng et al. | Double recovery and regeneration of Pt/C catalysts: Both platinum from the spent proton exchange membrane fuel cell stacks and carbon from the pomelo peel | |
| Guo et al. | The optimization of iron porphyrin@ MOF-5 derived FeNC electrocatalysts for oxygen reduction reaction in zinc-air batteries | |
| Chen et al. | Sulfur-induced electronic optimization of Mo5N6 for hydrogen evolution through topochemical substitution |
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 |