CN112717980A - Composite catalyst and preparation method and application thereof - Google Patents
Composite catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112717980A CN112717980A CN202011622970.7A CN202011622970A CN112717980A CN 112717980 A CN112717980 A CN 112717980A CN 202011622970 A CN202011622970 A CN 202011622970A CN 112717980 A CN112717980 A CN 112717980A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- molecular sieve
- composite
- water
- time
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 122
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 75
- 239000002808 molecular sieve Substances 0.000 claims abstract description 65
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910001868 water Inorganic materials 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000000725 suspension Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052680 mordenite Inorganic materials 0.000 claims description 4
- 235000011837 pasties Nutrition 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical group O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010981 drying operation Methods 0.000 claims 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 73
- 229910052697 platinum Inorganic materials 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 20
- 239000010410 layer Substances 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 239000010411 electrocatalyst Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a composite catalyst and a preparation method and application thereof. The preparation method of the composite catalyst comprises the following steps: (1) drying the suspension containing the graphene oxide and the Y-type molecular sieve, and carrying out reduction reaction under the inert atmosphere condition to obtain a reduced graphene oxide-Y-type molecular sieve composite material, namely an rGO-Y composite material; (2) dispersing the rGO-Y composite material in water to obtain a rGO-Y composite material suspension, the rGO-Y composite material suspension and H2PtCl6Mixing to obtain a mixed material A; and (3) reacting the mixed material A with a reducing agent to obtain the catalyst. The composite prepared by the inventionThe catalyst has stable structure, good dispersibility, difficult agglomeration and good conductivity; a small amount of catalyst platinum is loaded to obtain higher catalytic activity, the utilization rate of the catalyst platinum is high, and the catalytic performance is stable; the composite catalyst prepared by the invention can be effectively used for catalyzing the hydrogen production reaction by water electrolysis.
Description
Technical Field
The invention relates to a composite catalyst and a preparation method and application thereof.
Background
The development of chemicals based on clean energy and sustainable green raw materials is of great significance to the relief of problems such as environmental pollution and climate change caused by the use of fossil fuels. One prospective strategy is to convert atmospheric feedstocks of water, carbon dioxide, and nitrogen into important fuels or chemicals (including hydrogen, hydrocarbons, oxygenates, and ammonia, etc.) by coupling a renewable energy source (solar, wind, etc.) with an electrochemical process. In recent years, the cathodic process of water splitting (HER process) has attracted a high degree of attention as a sustainable source of clean energy, hydrogen. The product of the hydrogen production process by water electrolysis only contains hydrogen and oxygen, and no pollutant and carbon-containing compound are released; the method has simple process flow and simple and convenient operation, and is an ideal way for preparing high-purity hydrogen. The electrocatalyst plays a key role in the water electrolysis hydrogen production technology, and directly determines the reaction efficiency and the system energy consumption.
At present, platinum group noble metals (Pt, Ru, Pd, lr, etc.) are considered as the best electrocatalysts for cathode hydrogen production at low overpotential and high current density. However, the low natural reserves of precious metals present a high cost problem, limiting their widespread use in the electrolysis of water. The addition of the electrocatalyst carrier can not only improve the utilization rate of platinum and reduce cost, but also improve the activity of the catalyst. The size, dispersion and utilization efficiency of Pt nanoparticles in the electrocatalyst strongly depend on the catalyst support used and its surface properties. An ideal electrocatalyst support needs to satisfy the following conditions: (1) higher conductivity; (2) can be stably connected with the active component of the catalyst, and can not fall off; (3) higher specific surface area; (4) has a certain porous structure; (5) has excellent corrosion resistance.
Carbon is widely used as a catalyst carrier, wherein the carbon comprises Vulcan XC-72R carbon black (VC), Carbon Nanotubes (CNTs), Graphene (GE), Carbon Nanofibers (CNFs), and the like, wherein VC is most commonly used in commerce, and carbon black, which is a commonly used carrier at present, generally has a high specific surface area and good conductivity, is low in cost, and is easily available. However, carbon black particles also have some unavoidable problems when used as a carrier, and conductive carbon black generally has a pore size too small to accommodate platinum particles, so that the platinum particles are substantially adhered to the surface of the conductive carbon black; traditional carbon supported metal catalysts have poor stability and typically require high metal loadings to compensate for activity loss during long runs.
Graphene is a carbon material having a specific structure of a honeycomb shape, and its theoretical specific surface area (2630 m)2/g) and electrical conductivity (7200S/m) are much higher than other carbon materials. The two-dimensional structure of the graphene is beneficial to the uniform distribution of the platinum active component, and the capability of rapidly transferring electrons can be used for improving the electrode reaction speed. However, the two-dimensional structure of graphene still has limitations in the catalytic process, the graphene with a complete structure has high chemical stability, the surface of the graphene is in an inert state, and strong van der waals force exists between graphene sheets, so that aggregation is easy to generate and irreversible agglomeration occurs, and the specific surface area and specific capacity of the graphene are reduced.
The molecular sieve is a catalyst and a catalyst carrier material which are widely applied, and nano particles with different catalytic capacities can be compounded on the surface or in an open framework of the molecular sieve by an ion exchange method, a coprecipitation method, an impregnation method and the like. The molecular sieve microporous framework has larger specific surface area, which is beneficial to the uniform loading of active catalyst nano particles. However, molecular sieves have poor conductivity and are not suitable for direct use as a support for electrocatalysts.
Therefore, the development of a conductive material with stable structure, good dispersibility, difficult agglomeration and good conductivity is urgently needed in the field; the composite catalyst shows good catalytic performance with a small amount of supported platinum.
Disclosure of Invention
The invention aims to solve the technical problems of poor stability and dispersibility, easy agglomeration and poor conductivity of the composite catalyst in the prior art; the catalyst has the defects of low utilization rate, non-ideal catalytic performance and the like, and provides the composite catalyst and the preparation method and the application thereof. The composite catalyst prepared by the invention has the advantages of stable structure, good dispersibility, difficult agglomeration and good conductivity; a small amount of catalyst platinum is loaded to obtain higher catalytic activity, the utilization rate of the catalyst platinum is high, and the catalytic performance is stable; the composite catalyst prepared by the invention can be effectively used for catalyzing the hydrogen production reaction by water electrolysis.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of a composite catalyst, which specifically comprises the following steps:
(1) drying the suspension containing the graphene oxide and the Y-type molecular sieve, and carrying out reduction reaction under the inert atmosphere condition to obtain a reduced graphene oxide-Y-type molecular sieve composite material, namely an rGO-Y composite material;
(2) dispersing the rGO-Y composite material in water to obtain a rGO-Y composite material suspension, and mixing the rGO-Y composite material suspension with H2PtCl6Mixing to obtain a mixed material A; and reacting the mixed material A with a reducing agent to obtain the catalyst.
In the step (1), the graphene oxide may be an oxide of graphene conventionally used in the art.
In the step (1), the preparation method of the graphene oxide may be conventional in the art, and preferably is an improved Hummers method, and specifically includes the following steps: h2SO4、H3PO4、KMnO4Mixing the graphite and the graphite for the first time according to the mass ratio of 120:13:6:1, cooling to 35-40 ℃, and stirring at 50-55 ℃ to obtain a mixed material B; the mixed material B is sequentially mixed with ice water and H2O2Mixing the water solution for the second time, standing, centrifuging, collecting filter residue, and cleaning the filter residue to neutrality. The improved Hummers method adopted by the preferable graphene oxide preparation method of the invention can reduce the surface area of grapheneThe defect, promote the productivity, avoid the release of toxic gas.
Wherein, the graphite can be graphite conventionally used in the field, and is preferably flake graphite.
The stirring time can be the time conventionally used in the field, and generally can be 10-15 h, preferably 12-15 h.
Wherein, the stirring operation can further comprise a cooling operation, and the temperature can be generally reduced to room temperature.
The ice water may be a two-phase mixture of liquid water and solid water, which is conventionally considered by those skilled in the art.
Wherein, the mass ratio of the ice water to the graphite is conventional in the field, and is preferably (350-450): 1, more preferably 400: 1.
wherein, the H2O2H in aqueous solution2O2The mass percentage of (b) may be conventional in the art, and may be generally 20 to 35%, preferably 30 to 35%.
Wherein the graphite is in contact with the H2O2H in aqueous solution2O2The mass ratio of (A) can be conventional in the field, and generally can be (0.26-0.45): 1, preferably (0.30 to 0.45): 1.
the standing time can be the time of the operation routine in the field, and generally the solid phase and the liquid phase in the system can be completely separated, preferably 10-15 h, and more preferably 12-15 h.
Wherein the washing conditions and methods may be those conventional in such operations in the art, and generally comprise the steps of: and respectively washing the filter residue to be neutral by using absolute ethyl alcohol, HCl with the mass percent of 30% and deionized water.
Wherein, the operation of cleaning can further comprise the operation of drying. The drying conditions and methods may be those conventional in such operations in the art and may generally be carried out in a vacuum oven. The drying temperature can be the temperature which is conventional in the operation of the type in the field, and is preferably 50-60 ℃.
In the step (1), the Y-type molecular sieve can be a molecular sieve with a molar ratio of silicon element to aluminum element (1.5-3) which is conventionally considered by a person skilled in the art: 1, FAU structure molecular sieve.
In step (1), the preparation method of the Y-type molecular sieve can be conventional in the art, preferably a NaOH melt-hydrothermal method, and more preferably comprises the following steps: the mixture of the natural zeolite and NaOH is melted, mixed with water, aged and crystallized to obtain the product.
Wherein the natural zeolite can be clinoptilolite in Jinyun and/or mordenite in Jinyun, which are conventionally used in the art. Compared with the Y-type molecular sieve prepared by taking silica sol and activated alumina as raw materials conventionally adopted in the field, the Y-type molecular sieve prepared by taking the natural zeolite as the raw material has low cost and simple preparation process.
Wherein, the mole ratio of silicon element and aluminum element in the natural zeolite can be conventional in the field, and is preferably (4.5-6): 1.
wherein the mass ratio of the natural zeolite to the NaOH may be conventional in the art, preferably 1: (1.2-1.3).
Wherein, the melting conditions and method can be the conditions and method which are conventional in the operation in the field, and the framework structure of the natural zeolite can be generally melted.
The melting temperature may be a temperature conventionally used in the art, and is preferably 500 to 650 ℃, and more preferably 550 to 600 ℃.
The melting time can be the time of the operation routine in the field, and is preferably 1.5 to 2.5 hours, and more preferably 2 to 2.5 hours.
Wherein, the mass ratio of the material prepared after melting to the water can be conventional in the field, and is preferably 1: (4-5), more preferably 1: (4.5-5).
Wherein the aging time can be the time of the operation routine in the field, preferably 10-14 h, more preferably 12-14 h.
The crystallization temperature may be a temperature conventionally used in the art, and is preferably 90 to 110 ℃, and more preferably 100 to 110 ℃.
The crystallization time can be the time of the conventional operation in the field, preferably 6 to 10 hours, and more preferably 8 to 10 hours.
Wherein, the crystallization operation can further comprise the operations of water washing and/or drying. The drying temperature can be the temperature conventional in the operation in the field, and is preferably 140-160 ℃. The drying time can be the time conventionally used in the art, and is preferably 1.5 to 2.5 hours, and more preferably 2 to 2.5 hours.
In the step (1), the mass ratio of the graphene oxide to the Y-type molecular sieve may be conventional in the art, and is preferably 1: (4-6), more preferably 1: (4.5-5).
In the step (1), in the suspension containing graphene oxide and the Y-type molecular sieve, the concentration of the graphene oxide may be conventional in the art, and is preferably 4-6 mg/mL, and more preferably 5 mg/mL. As is conventional in the art, a mixture in which the substance distributed in the liquid material is not dissolved but merely dispersed is referred to as a suspension.
In step (1), the preparation method of the suspension containing graphene oxide and Y-type molecular sieve may be conventional in the art, and may generally include the following steps: (a) dispersing the graphene oxide in water to obtain graphene oxide gel; (b) and dispersing the Y-type molecular sieve in the graphene oxide gel.
In step (a), the dispersing method may be a method conventional in such operations in the art, and may be ultrasonic dispersing in general.
In step (a), the dispersion time may be a time conventional in the operation in the field, and generally, the graphene oxide may be uniformly dispersed in the water.
Wherein, in the step (b), the dispersing method can be a method which is conventional in the operation in the field, and can be ultrasonic dispersing generally.
In the step (b), the dispersing time may be a time conventionally used in the art, and generally the Y-type molecular sieve may be uniformly dispersed in the graphene oxide gel, preferably 15 to 20min, and more preferably 20 min.
Wherein, in the step (b), the operation of dispersing can be further followed by the operation of stirring. The rotation speed of the stirring can be the rotation speed of the operation in the field, preferably 800-1200 turns/min, and more preferably 1000-1100 turns/min. The stirring time can be the time conventionally used in the field, preferably 25-35 min, more preferably 30-35 min.
In step (1), the conditions and methods of drying may be those conventional in such operations in the art, and generally include the following steps: stirring the mixture at 75-85 ℃ until the mixture is pasty, and drying the pasty mixture in an oven at the temperature of 45-50 ℃ to obtain the product.
In step (1), the inert atmosphere may be an inert atmosphere conventionally used in the art, for example, nitrogen.
In step (1), the conditions and method of the reduction reaction may be conventional in the art, and generally the graphene oxide may be reduced to reduced graphene oxide.
In the step (1), the temperature of the reduction reaction may be a temperature conventional in the art, preferably 350 to 450 ℃, and more preferably 380 to 400 ℃.
In the step (1), the time of the reduction reaction may be a time conventionally used in the art, and is preferably 1.5 to 2.5 hours, and more preferably 2 to 2.5 hours.
In step (1), the reduction reaction may be further followed by cooling, which may be generally to room temperature.
In the step (2), the mass-to-volume ratio of the rGO-Y composite material to the water may be conventional in the art, and is preferably 0.4 to 0.6mg/mL, more preferably 0.5 to 0.6 mg/mL.
In the step (2), the rGO-Y composite material and H2PtCl6The mass ratio of the Pt element(s) in (b) may be conventional in the art, and is preferably 1: (0.6-1), more preferably 1: (0.7-0.8).
In step (2), the reducing agent may be H which is conventionally used in the art2PtCl6Reducing agent for reduction to Pt metal, preferably NaHB4And/or hydrazine hydrate, more preferably NaHB4。
Wherein, when the reducing agent is NaBH4When, the NaBH4Can be prepared as NaBH according to the routine method in the field4Added as an aqueous solution. Wherein, the NaBH4NaBH in aqueous solution4The concentration of (b) is a conventional concentration in the art, preferably 0.04-0.06 mol/L, more preferably 0.05-0.06 mol/L.
In the step (2), the molar ratio of the mass of the rGO-Y composite material to the reducing agent can be conventional in the art, preferably 3-5 g/mol, and more preferably 3-4 g/mol.
In step (2), the method of dispersion may be conventional in the art, and may be generally ultrasonic dispersion.
In the step (2), the dispersing time can be conventional in the art, and generally the rGO-Y composite material can be uniformly dispersed in the water, preferably 0.5 to 1.5 hours, and more preferably 1 hour.
In step (2), the mixing method may be a method conventional in such operations in the art, and may be generally an ultrasonic dispersion method.
In the step (2), the mixing time may be a time conventionally used in the art, and is preferably 35 to 45min, and more preferably 40 to 45 min.
In step (2), the method for adding the reducing agent may be conventional in the art, and may be generally dropwise.
In step (2), the reaction may be H on the surface and/or inside the rGO-Y composite material as conventionally considered by those skilled in the art2PtCl6A reaction of reducing the reducing agent to Pt metal.
In the step (2), the reaction time can be the time conventionally used in the reaction in the field, and is preferably 6-8 h.
In the step (2), the reaction operation may further include one or more of centrifuging, collecting the residue, washing, and drying.
The washing conditions and method may be those commonly used in the art, and the washing may be generally performed using distilled water.
The drying temperature may be a temperature conventionally used in the art, and is preferably 35 to 45 ℃, and more preferably 40 to 45 ℃.
The drying time can be the time of the operation routine in the field, preferably 20-30 h, and more preferably 24-30 h.
The invention also provides a composite catalyst, which is prepared by the preparation method of the composite catalyst.
The invention also provides an application of the composite catalyst as a cathode catalyst in the field of proton exchange membrane fuel cells.
Preferably, the composite catalyst is used as a cathode catalyst in the field of hydrogen preparation by water electrolysis through a proton exchange membrane.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: and compounding the graphene oxide and the Y-type molecular sieve, and loading metal Pt to prepare the composite catalyst containing the reduced graphene oxide, the Y-type molecular sieve and the Pt metal catalyst. In the research and development process, the Y-type molecular sieve is compounded between layers of the reduced graphite oxide as a filling material to prevent the stacking of the reduced graphene oxide interlayer and prevent the agglomeration of the reduced graphene oxide carrier; the reduced graphene oxide is wrapped on the surface of the Y-shaped molecular sieve, so that the conductivity of the Y-shaped molecular sieve can be obviously improved, and the complementary advantages of the Y-shaped molecular sieve and the Y-shaped molecular sieve can be realized. The Y-type molecular sieve has a porous structure, so that the stability and the dispersion uniformity of the supported catalyst platinum are ensured, and a synergistic effect is achieved between the Y-type molecular sieve and the catalyst platinum; in the composite catalyst prepared by the invention, the number of active sites of platinum is increased, compared with the prior art, the utilization rate of the platinum catalyst is greatly improved, ideal catalytic performance can be realized by adopting a small amount of platinum catalyst, the cost of the composite catalyst is reduced, the catalytic performance is stable, and the initial voltage is still maintained at 98% after 1000 times of circulation.
Drawings
FIG. 1 is a LSV polarization curve of the composite catalysts prepared in examples 1-2 and comparative examples 1-2;
FIG. 2 is a graph showing the Tafel slopes of the composite catalysts prepared in examples 1 to 2 and comparative examples 1 to 2;
FIG. 3 is a CV curve of the composite catalyst prepared in example 1 at various sweep rates;
FIG. 4 is a CV curve of the composite catalyst prepared in example 2 at various sweep rates;
FIG. 5 is a CV curve of the composite catalyst prepared in comparative example 1 at various sweep rates;
FIG. 6 is a CV curve of the composite catalyst prepared in comparative example 2 at various sweep rates;
FIG. 7 is a graph showing the relationship between the current density of the composite catalysts obtained in examples 1 to 2 and comparative examples 1 to 2 and the change in the scanning rate;
FIG. 8 is an SEM photograph of the composite catalyst prepared in example 1;
fig. 9 is an XRD pattern of the composite catalyst prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
(1) Preparation of graphene oxide by improved Hummers method
First, H2SO4、H3PO4、KMnO4Mixing the graphite powder and the crystalline flake graphite according to the mass ratio of 120:13:6:1, slightly releasing heat to 35-40 ℃, heating to 50 ℃, stirring for 12 hours, and cooling the product to room temperature; pouring ice water into the reaction kettle, and then adding 30 mass percent of H2O2Aqueous solution, flake graphite and H2O2H in aqueous solution2O2Is 0.3: 1, the product was observed to turn to dark yellow; standing for 12h, centrifuging, collecting the residue, and separatingWashing the filter residue to be neutral by using absolute ethyl alcohol, 30% HCl and deionized water, and drying in vacuum at 60 ℃ to obtain graphene oxide;
(2) preparation of Y-type molecular sieve by using natural zeolite as raw material
Jinyun mordenite (silicon to aluminium ratio 5.1: 1) and NaOH were mixed at a ratio of 7.5: 9, uniformly mixing in a nickel crucible, and melting for 2 hours at 550 ℃; adding a certain amount of water (the solid-liquid mass ratio is 1:4.5) into the molten product, uniformly mixing, stirring and aging in a plastic beaker for 12 hours, then transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing at 100 ℃ for 8 hours; repeatedly washing the product with deionized water during suction filtration, and drying at 150 ℃ for 2 h;
(3) preparation of reduced graphene oxide-Y type molecular sieve composite material (rGO-Y composite material)
Adding a dispersed graphene oxide suspension with the concentration of 5mg/mL into the Y-type molecular sieve (the mass ratio of the graphene oxide to the Y-type molecular sieve is 1:5), carrying out ultrasonic dispersion for 20min, and then strongly stirring for 30min to obtain a suspension containing the graphene oxide and the Y-type molecular sieve; then, continuously stirring the suspension containing the graphene oxide and the Y-type molecular sieve at 80 ℃ to evaporate water, and drying the obtained paste in an oven at 45 ℃; finally, firing for 2h at 380 ℃ under the protection of nitrogen, and naturally cooling the obtained product to room temperature to obtain the reduced graphene oxide-Y type molecular sieve composite material (rGO-Y composite material);
(4) preparation of rGO-Y composite material loaded Pt composite catalyst
Dispersing 5mg of the newly prepared rGO-Y composite material obtained in the step (3) in 10mL of water, performing ultrasonic dispersion for 1H, and then adding 8.4mg of H2PtCl6(the mass of Pt contained in the solution is 4mg), and continuing to perform ultrasonic treatment for 40 min; then, 30mL of NaBH with a concentration of 0.05mol/L was added dropwise with stirring4Stirring the solution for 8 hours to ensure that the solution fully reacts; and finally, centrifugally separating the product, collecting filter residues, repeatedly washing the filter residues by using distilled water, and drying the product at 40 ℃ for 24 hours in vacuum to obtain the composite catalyst. The amount of platinum carried in the composite catalyst obtained in this example was analyzed by ICP, and the result of the test was 44%, and the scanning electron micrograph thereof is shown in fig. 8. The XRD pattern is shown in FIG. 9, and it can be seen from FIG. 9And after the rGO is coated, the structure of the Y-type molecular sieve is not influenced, because the content of the rGO is less, the diffraction peak of the Y-type molecular sieve covers the diffraction peak of the rGO, and therefore the characteristic absorption peak of the rGO cannot be observed.
Example 2
(1) Preparation of Graphene Oxide (GO) by improved Hummers method
First, H2SO4、H3PO4、KMnO4Mixing the graphite powder and the crystalline flake graphite according to the mass ratio of 120:13:6:1, slightly releasing heat to 35-40 ℃, heating to 50 ℃, stirring for 12 hours, and cooling the product to room temperature; pouring ice water into the reaction kettle, and then adding 30 mass percent of H2O2Aqueous solution, flake graphite and H2O2H in aqueous solution2O2Is 0.3: 1, the product was observed to turn to dark yellow; standing for 12h, centrifugally separating and collecting filter residues, respectively washing the filter residues to be neutral by using absolute ethyl alcohol, 30% HCl and deionized water, and drying in vacuum at 60 ℃ to obtain graphene oxide;
(2) preparation of Y-type molecular sieve by using natural zeolite as raw material
Clinoptilolite in Jinyun (silicon to aluminum ratio of 5.4: 1) and NaOH in a ratio of 7.5: 9, uniformly mixing in a nickel crucible, and melting for 2 hours at 550 ℃; adding a certain amount of water (the solid-liquid mass ratio is 1:4.5) into the molten product, uniformly mixing, stirring and aging in a plastic beaker for 12 hours, then transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing at 100 ℃ for 8 hours; repeatedly washing the product with deionized water during suction filtration, and drying at 150 ℃ for 2 h;
(3) preparation of reduced graphene oxide-Y type molecular sieve composite material (rGO-Y composite material)
Adding a dispersed graphene oxide suspension with the concentration of 5mg/mL into the Y-type molecular sieve (the mass ratio of the graphene oxide to the Y-type molecular sieve is 1:4.5), carrying out ultrasonic dispersion for 20min, and then strongly stirring for 30min to obtain a suspension containing the graphene oxide and the Y-type molecular sieve; then, continuously stirring the suspension containing the graphene oxide and the Y-type molecular sieve at 80 ℃ to evaporate water, and drying the obtained paste in an oven at 45 ℃; finally, firing for 2h at 380 ℃ under the protection of nitrogen, and naturally cooling the obtained product to room temperature to obtain the reduced graphene oxide-Y type molecular sieve composite material (rGO-Y composite material);
(4) preparation of rGO-Y composite material loaded Pt composite catalyst
Dispersing 5mg of the newly prepared rGO-Y composite material obtained in the step (3) in 10mL of water, performing ultrasonic dispersion for 1H, and then adding 7.35mg of H2PtCl6(the mass of Pt contained in the solution is 3.5mg), and continuing to perform ultrasonic treatment for 40 min; then, 25mL of NaBH of 0.05mol/L concentration was added dropwise with stirring4Stirring the solution for 8 hours to ensure that the solution fully reacts; and finally, centrifugally separating the product, collecting filter residues, repeatedly washing the filter residues by using distilled water, and drying the product at 40 ℃ for 24 hours in vacuum to obtain the composite catalyst. The amount of platinum carried in the composite catalyst obtained in this example was analyzed by ICP, and the result of the test was 41%.
Comparative example 1
An imported brand of commercial platinum carbon catalyst having a carrier of XC-72R carbon black and a platinum loading of 60% as measured by ICP was purchased as a comparative example. The amount of platinum carried was higher, unlike examples 1 and 2.
Comparative example 2
(1) Preparation of Y-type molecular sieve by using natural zeolite as raw material
Jinyun mordenite (silicon to aluminium ratio 5.1: 1) and NaOH were mixed at a ratio of 7.5: 9, uniformly mixing in a nickel crucible, and melting for 2 hours at 550 ℃; adding a certain amount of water (the solid-liquid mass ratio is 1:4.5) into the molten product, uniformly mixing, stirring and aging in a plastic beaker for 12 hours, then transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing at 100 ℃ for 8 hours; repeatedly washing the product with deionized water during suction filtration, and drying at 150 ℃ for 2 h;
(2) preparation of graphene-Y type molecular sieve composite material (GE-Y composite material) A well-dispersed Graphene (GE) dispersion liquid with the concentration of 5mg/mL (GE and Y type molecular sieve are mixed according to the mass ratio of 1:5) is added into a Y type molecular sieve, the thickness of graphene is 1-5 nm, and after ultrasonic dispersion is carried out for 20min, strong stirring is carried out for 30min, so that uniform suspension is obtained. The suspension was then continuously stirred at 80 ℃ to evaporate water, and the resulting paste was dried in an oven at 45 ℃. And finally, firing for 2h at 380 ℃ under the protection of nitrogen, and naturally cooling the obtained product to room temperature to obtain the graphene-Y type molecular sieve composite material (GE-Y composite material).
(3) Preparation of composite catalyst of GE-Y composite material loaded with Pt
5mg of the GE-Y composite material newly prepared in the step (2) is dispersed in 10mL of water, ultrasonic dispersion is carried out for 1h, and 8.4mgH is added2PtCl6(the mass of Pt contained in the solution is 4mg), and continuing to perform ultrasonic treatment for 40 min; then, 30mL of NaBH with a concentration of 0.05mol/L was added dropwise with stirring4Stirring the solution for 8 hours to ensure that the solution fully reacts; and finally, centrifugally separating the product, collecting filter residues, repeatedly washing the filter residues by using distilled water, and drying the product at 40 ℃ for 24 hours in vacuum to obtain the composite catalyst.
Comparative example 3
Compared with the example 1, the difference is only that the material adding sequence in the step (3) and the step (4) is different, specifically:
the steps (1) and (2) are the same as in example 1;
(3) preparation of Y-type molecular sieve-Pt composite material (Y-Pt composite material)
Dispersing 4mg of the newly prepared Y-type molecular sieve in the step (2) in 10mL of water, performing ultrasonic dispersion for 1H, and then adding 8.4mg of H2PtCl6(the mass of Pt contained in the solution is 4mg), and continuing to perform ultrasonic treatment for 40 min; then, 30mL of NaBH with a concentration of 0.05mol/L was added dropwise with stirring4Stirring the solution for 8 hours to ensure that the solution fully reacts; finally, centrifuging the product, collecting filter residue, repeatedly cleaning the filter residue with distilled water, and vacuum-drying the product at 40 ℃ for 24 hours to obtain the Y-Pt composite material;
(4) preparation of composite catalyst
Adding a dispersed graphene oxide suspension with the concentration of 5mg/mL (the mass ratio of graphene oxide to the Y-type molecular sieve is 1:5) into the Y-Pt composite material prepared in the step (3), carrying out ultrasonic dispersion for 20min, and then strongly stirring for 30min to obtain a suspension; then, continuously stirring the suspension at 80 ℃ to evaporate water, and placing the obtained paste in a drying oven to be dried at 45 ℃; and finally, burning for 2h at 380 ℃ under the protection of nitrogen, and naturally cooling the obtained product to room temperature to obtain the composite material.
The composite material prepared by the comparative example has no Pt active site on graphene, and the overpotential (eta @10mA · cm) of the composite material is tested-2geo) was 183.5mV, much higher than example 1, and the composite catalyst prepared by this comparative example had poor catalytic performance.
Comparative example 4
Compared with the example 1, the difference is only that the material adding sequence in the step (3) and the step (4) is different, specifically:
the steps (1) and (2) are the same as in example 1;
(3) preparation of graphene oxide-Pt composite material (GO-Pt composite material)
Dispersing 1mg of graphene oxide newly prepared in the step (1) in 10mL of water, performing ultrasonic dispersion for 1H, and then adding 8.4mg of H2PtCl6(the mass of Pt contained in the solution is 4mg), and continuing to perform ultrasonic treatment for 40 min; then, 30mL of NaBH with a concentration of 0.05mol/L was added dropwise with stirring4Stirring the solution for 8 hours to ensure that the solution fully reacts; finally, centrifugally separating the product, collecting filter residue, repeatedly washing the filter residue with distilled water, and vacuum-drying the product at 40 ℃ for 24 hours;
(4) preparation of composite catalyst
Adding a dispersed GO-Pt composite material suspension into a Y-type molecular sieve, wherein the concentration of graphene oxide in the GO-Pt composite material suspension is 5mg/mL, the mass ratio of the graphene oxide to the Y-type molecular sieve is 1:5, and after ultrasonic dispersion is carried out for 20min, strongly stirring for 30min to obtain a GO-Pt composite material and Y-type molecular sieve suspension; then, continuously stirring the GO-Pt composite material and the suspension of the Y-type molecular sieve at 80 ℃ to evaporate water, and drying the obtained paste in a drying oven at 45 ℃; and finally, burning for 2h at 380 ℃ under the protection of nitrogen, and naturally cooling the obtained product to room temperature to obtain the composite material.
In the preparation process of the composite material prepared by the comparative example, the phenomenon that graphene oxide is easy to agglomerate is found, the load of Pt is small, a large amount of Pt is difficult to uniformly load on the surface of a small amount of GO, and the overpotential (eta @10 mA-cm) of the composite material is tested-2geo) was 210.3mV, and the catalytic performance of the composite catalyst prepared in this comparative example was poor.
Effect example 1
(1) Electrode preparation
Electrochemical tests were performed at room temperature using an electrochemical workstation (autolab, wangton, switzerland). A standard three-electrode system was used in the test with a glassy carbon disk electrode (5 mm diameter, 0.204mg cm loading)-2) As a working electrode, a platinum electrode was used as a counter electrode and an Ag/AgCl (3M KCl) electrode was used as a reference electrode. With Al2O3The powder mechanically polished the working electrode and then washed with ethanol and deionized water, respectively. The working electrode slurry was prepared as follows: 2mg of the catalyst was dispersed in 500. mu.L of a mixed solvent of water and isopropyl alcohol at a volume ratio of 4:1, and after adding 20. mu.L of Nafion solution (5%), the solution was ultrasonically dispersed for 3 hours to form a uniform slurry, wherein the catalyst was any one of the composite catalysts prepared in examples 1-2 and comparative examples 1-2. And uniformly dripping 10 mu L of slurry on the surface of the glassy carbon electrode, and naturally airing to obtain the working electrode.
(2) And respectively scanning the prepared working electrode for 30-50 times by a cyclic voltammetry until the signal is stable, collecting data, and calculating to obtain overpotential, Tafel slope, electric double layer capacitance and cyclic performance data.
1. Measuring overpotential (eta @10mA · cm)-2geo)
The overpotential eta is an important parameter for measuring the catalytic activity of the composite catalyst, and the smaller the eta value is, the lower the actual voltage required by the current density is, and the relatively smaller the energy consumption is, which shows that the better the electrocatalysis performance is, and the higher the catalytic activity of the composite catalyst is. In order to quantitatively compare the performances of the composite catalysts, the current density of 10mA cm is selected-2The results of comparing the catalytic performances of different composite catalysts with corresponding overpotential values are shown in Table 1.
2. Linear Sweep Voltammetry (LSV)
The Linear Sweep Voltammetry (LSV) test is to adopt each working electrode prepared in the step (1) respectively in 0.5M H electrolyte2SO4In solution at 2mV · s-1The scan rate was tested to obtain an LSV polarization curve, the results of which are shown in fig. 1.
The Tafel slope (Tafel slope) is obtained from the LSV polarization curve, which reflects the kinetics of the electrochemical reaction. A tafel curve is obtained by redrawing the LS polarization curve (logarithmic plot of overpotential versus current density), which is shown in fig. 2, and then the tafel equation can be fitted according to the linear part of the tafel curve:
η＝a+b·log j
where η represents the overpotential, b represents the tafel slope, and j represents the current density. Tafel slope data is shown in Table 1, where a smaller Tafel slope indicates a faster increase in current density, indicating that the rate-determining step is at the end of the multiple electron transfer reaction, which is generally a good indicator of electrocatalyst.
3. Electrochemical active area (ECSA)
The electrochemical active specific surface area is one of important indexes for measuring the catalytic performance of the composite catalyst, and the electrochemical active surface area is measured by the capacitance value (C) of an electric double layerdl) Measured by the value of the capacitance of the electric double layer (C) at the solid-liquid interfacedl) Is in direct proportion.
CdlThe test method comprises the following steps: under the potential window without Faraday process, at different sweeping speeds (10-100 mV. multidot.s)-1) For testing, 5-8 continuous scanning speeds are usually selected. The obtained Cyclic Voltammetry (CV) curve gradually takes a rectangular shape with the increase of the sweep rate, and in order to make the obtained data linear, the appropriate sweep rate needs to be selected. In the present effective example, 5 different sweep rates (10, 30, 50, 70, and 90mV · s) were used in a certain potential interval to obtain electric double layer capacitance data-1) The CV curves of the composite catalysts prepared in example 1, example 2, comparative example 1 and comparative example 2 at different sweep rates were shown in fig. 3 to 6, respectively, by performing cyclic voltammetry. Then, respectively counting the difference (Δ j ═ ja-jc) between the current densities of the anode and the cathode corresponding to the same overpotential value (usually, the middle value of the selected voltage range) at different sweep rates, plotting with the sweep rate as the abscissa and the difference between the current densities as the ordinate, and performing linear regression fitting on the plotted plot to obtain the slope of the fitting equation, wherein one half of the slope is the capacitance value of the electric double layer, and the curve showing the relationship between the current density of the composite catalysts prepared in examples 1 to 2 and comparative examples 1 to 2 and the change of the scanning rate is shown in fig. 7, and the electric double layer is shown in fig. 7The capacitance results are shown in table 1. The larger the electric double layer capacitance is, the larger the active specific surface area and the more active sites of the catalyst are, and therefore, the catalyst has stronger catalytic activity.
4. Cycle performance test
Working electrodes made using the composite catalysts prepared in examples 1 and 2 above, at 2 mV. multidot.s-1The scanning speed of the composite catalyst is 1000 times of cyclic scanning, and the result shows that the polarization curve of the composite catalyst has only slight change, and the initial voltage still maintains 98 percent.
TABLE 1
| Composite catalyst | Overpotential (eta @10mA · cm)-2geo) | Tafel slope | Double electric layer capacitor |
| Example 1 | 37.1mV | 27.4mV/dec | 59.98mF/cm2 |
| Example 2 | 44.7mV | 36.7mV/dec | 55.49mF/cm2 |
| Comparative example 1 | 48.7mV | 39.4mV/dec | 30.65mF/cm2 |
| Comparative example 2 | 53.7mV | 40.7mV/dec | 20.6mF/cm2 |
As is clear from the data in table 1 and fig. 1 to 7, the overpotential and tafel slope of the catalyst are reduced and the electric double layer capacitance of the catalyst is increased as compared with the commercial catalyst. The result shows that the compounding of the graphene and the Y-type molecular sieve is beneficial to stable and uniform dispersion of platinum nanoparticles, the utilization efficiency of platinum can be improved, and the ideal catalytic performance can be obtained under the condition of low platinum loading.
Claims (10)
1. The preparation method of the composite catalyst is characterized by comprising the following steps:
(1) drying the suspension containing the graphene oxide and the Y-type molecular sieve, and carrying out reduction reaction under the inert atmosphere condition to obtain a reduced graphene oxide-Y-type molecular sieve composite material, namely an rGO-Y composite material;
(2) dispersing the rGO-Y composite material in water to obtain a rGO-Y composite material suspension, and mixing the rGO-Y composite material suspension with H2PtCl6Mixing to obtain a mixed material A; and reacting the mixed material A with a reducing agent to obtain the catalyst.
2. The method for preparing the composite catalyst according to claim 1, wherein the method for preparing graphene oxide comprises the following steps: h2SO4、H3PO4、KMnO4Mixing the graphite and the graphite for the first time according to the mass ratio of 120:13:6:1, cooling to 35-40 ℃, and stirring at 50-55 ℃ to obtain a mixed material B; the mixed material B is sequentially mixed with ice water and H2O2Mixing the water solution for the second time, standing, centrifuging to collect the residue, and cleaningFiltering the filter residue to be neutral;
preferably, the graphite is flake graphite;
preferably, the stirring time is 10-15 h, more preferably 12-15 h;
preferably, the stirring operation further comprises a cooling operation, more preferably a cooling operation to room temperature;
preferably, the mass ratio of the ice water to the graphite is (350-450): 1, more preferably 400: 1;
preferably, said H2O2H in aqueous solution2O2The mass percent of (A) is 20-35%, more preferably 30-35%;
preferably, the graphite and the H2O2H in aqueous solution2O2The mass ratio of (0.26-0.45): 1, more preferably (0.30 to 0.45): 1;
preferably, the standing time is 10-15 h, more preferably 12-15 h;
preferably, the cleaning comprises the following steps: washing the filter residue to be neutral by using absolute ethyl alcohol, 30 mass percent of HCl and deionized water respectively;
preferably, the operation of cleaning further comprises an operation of drying.
3. The method for preparing the composite catalyst according to claim 1, wherein the Y-type molecular sieve is prepared by NaOH fusion-hydrothermal method in step (1), and preferably comprises the following steps: melting a mixture of natural zeolite and NaOH, mixing with water, aging and crystallizing to obtain the product;
preferably, the natural zeolite is clinoptilolite in Jinyun and/or mordenite in Jinyun;
preferably, the mole ratio of the silicon element to the aluminum element in the natural zeolite is (4.5-6): 1;
preferably, the mass ratio of the natural zeolite to the NaOH is 1: (1.2-1.3);
preferably, the melting temperature is 500-650 ℃, more preferably 550-600 ℃;
preferably, the melting time is 1.5 to 2.5 hours, more preferably 2 to 2.5 hours;
preferably, the mass ratio of the material prepared after melting to the water is 1: (4-5), more preferably 1: (4.5-5);
preferably, the aging time is 10-14 h, more preferably 12-14 h;
preferably, the crystallization temperature is 90-110 ℃, more preferably 100-110 ℃;
preferably, the crystallization time is 6 to 10 hours, and more preferably 8 to 10 hours;
preferably, the crystallization operation further comprises a water washing and/or drying operation; preferably, the drying temperature is 140-160 ℃; preferably, the drying time is 1.5 to 2.5 hours, and more preferably 2 to 2.5 hours.
4. The preparation method of the composite catalyst according to claim 1, wherein in the step (1), the mass ratio of the graphene oxide to the Y-type molecular sieve is 1: (4-6);
and/or in the step (1), in the suspension containing the graphene oxide and the Y-type molecular sieve, the concentration of the graphene oxide is 4-6 mg/mL;
and/or in the step (1), the drying operation comprises the following steps: stirring the mixture at 75-85 ℃ until the mixture is pasty, and drying the pasty mixture in an oven at the temperature of 45-50 ℃ to obtain the product;
and/or, in the step (1), the inert atmosphere is nitrogen;
and/or in the step (1), the temperature of the reduction reaction is 350-450 ℃;
and/or in the step (1), the time of the reduction reaction is 1.5-2.5 h;
and/or, in the step (1), the operation of the reduction reaction is further followed by a cooling operation.
5. The preparation method of the composite catalyst according to claim 4, wherein in the step (1), the mass ratio of the graphene oxide to the Y-type molecular sieve is 1: (4.5-5);
and/or in the step (1), in the suspension containing the graphene oxide and the Y-type molecular sieve, the concentration of the graphene oxide is 5 mg/mL;
and/or in the step (1), the temperature of the reduction reaction is 380-400 ℃;
and/or in the step (1), the time of the reduction reaction is 2-2.5 h;
and/or in the step (1), the cooling operation is cooling to room temperature.
6. The method for preparing the composite catalyst according to claim 1, wherein in the step (1), the method for preparing the suspension containing the graphene oxide and the Y-type molecular sieve comprises the following steps: (a) dispersing the graphene oxide in water to obtain graphene oxide gel; (b) dispersing the Y-type molecular sieve in the graphene oxide gel;
preferably, in step (a), the dispersing method is ultrasonic dispersing;
preferably, in step (b), the dispersing method is ultrasonic dispersing;
preferably, in the step (b), the dispersing time is 15-20 min, and more preferably 20 min;
preferably, in step (b), the dispersing operation is further followed by stirring operation; preferably, the rotation speed of the stirring is 800-1200 turns/min, more preferably 1000-1100 turns/min; preferably, the stirring time is 25-35 min, more preferably 30-35 min.
7. The method for preparing the composite catalyst according to any one of claims 1 to 6, wherein in the step (2), the mass-to-volume ratio of the rGO-Y composite material to the water is 0.4 to 0.6mg/mL, preferably 0.5 to 0.6 mg/mL;
and/or, in step (2), the rGO-Y composite material and H2PtCl6The mass ratio of the Pt elements is 1: (0.6-1), preferably 1: (0.7-0.8);
and/or, in the step (2), the reducing agent is NaHB4And/or hydrazine hydrate, preferably NaHB4(ii) a When the reducing agent is NaBH4When, the NaBH4With NaBH4Added as an aqueous solution, the NaBH4NaBH in aqueous solution4The concentration of (b) is preferably 0.04 to 0.06mol/L, more preferably 0.05 to 0.06 mol/L;
and/or in the step (2), the molar ratio of the mass of the rGO-Y composite material to the reducing agent is 3-5 g/mol, preferably 3-4 g/mol;
and/or in the step (2), the dispersing method is ultrasonic dispersing;
and/or in the step (2), the dispersing time is 0.5-1.5 h, preferably 1 h;
and/or in the step (2), the mixing method is an ultrasonic dispersion method;
and/or, in the step (2), the mixing time is 35-45 min, preferably 40-45 min;
and/or, in the step (2), the addition method of the reducing agent is dropwise adding;
and/or in the step (2), the reaction time is 6-8 h;
and/or, in the step (2), the reaction operation further comprises any one or more of operations of centrifugally collecting filter residues, washing and drying; preferably, the washing method is to use distilled water to carry out the washing; preferably, the drying temperature is 35-45 ℃, more preferably 40-45 ℃; preferably, the drying time is 20 to 30 hours, and more preferably 24 to 30 hours.
8. A composite catalyst prepared by the method for preparing the composite catalyst according to any one of claims 1 to 7.
9. Use of the composite catalyst of claim 8 as a cathode catalyst in the field of proton exchange membrane fuel cells.
10. The application of the composite catalyst as a cathode catalyst in the field of hydrogen preparation by water electrolysis through a proton exchange membrane is characterized in that the composite catalyst is applied to the field of hydrogen preparation through water electrolysis through the proton exchange membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011622970.7A CN112717980B (en) | 2020-12-31 | 2020-12-31 | Composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011622970.7A CN112717980B (en) | 2020-12-31 | 2020-12-31 | Composite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112717980A true CN112717980A (en) | 2021-04-30 |
| CN112717980B CN112717980B (en) | 2023-09-15 |
Family
ID=75609017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011622970.7A Active CN112717980B (en) | 2020-12-31 | 2020-12-31 | Composite catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112717980B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113908830A (en) * | 2021-09-23 | 2022-01-11 | 西安交通大学 | Supported noble metal catalyst, preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101814607A (en) * | 2010-04-17 | 2010-08-25 | 上海交通大学 | Preparation method of platinum/graphen catalyst for proton exchange membrane fuel cell |
| KR20130100071A (en) * | 2013-07-26 | 2013-09-09 | 건국대학교 산학협력단 | A method for preparing pt-zsm-5 |
| CN105833889A (en) * | 2016-03-21 | 2016-08-10 | 武汉理工大学 | Platinum supported catalyst based on porous graphene/nano ceramic sandwiched structure and preparation method thereof |
| WO2018151228A1 (en) * | 2017-02-15 | 2018-08-23 | 旭化成株式会社 | Negative electrode, method for producing same, electrolytic cell using same, and hydrogen production method |
| CN109167069A (en) * | 2018-07-17 | 2019-01-08 | 常州大学 | A kind of high activity electrode preparation method of Metal Supported on the binary vector containing molecular sieve |
-
2020
- 2020-12-31 CN CN202011622970.7A patent/CN112717980B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101814607A (en) * | 2010-04-17 | 2010-08-25 | 上海交通大学 | Preparation method of platinum/graphen catalyst for proton exchange membrane fuel cell |
| KR20130100071A (en) * | 2013-07-26 | 2013-09-09 | 건국대학교 산학협력단 | A method for preparing pt-zsm-5 |
| CN105833889A (en) * | 2016-03-21 | 2016-08-10 | 武汉理工大学 | Platinum supported catalyst based on porous graphene/nano ceramic sandwiched structure and preparation method thereof |
| WO2018151228A1 (en) * | 2017-02-15 | 2018-08-23 | 旭化成株式会社 | Negative electrode, method for producing same, electrolytic cell using same, and hydrogen production method |
| EP3388553A1 (en) * | 2017-02-15 | 2018-10-17 | Asahi Kasei Kabushiki Kaisha | Negative electrode, method for producing same, electrolytic cell using same, and hydrogen production method |
| CN109167069A (en) * | 2018-07-17 | 2019-01-08 | 常州大学 | A kind of high activity electrode preparation method of Metal Supported on the binary vector containing molecular sieve |
Non-Patent Citations (3)
| Title |
|---|
| BRADLEY LADEWIG等主编: "《低温燃料电池材料》", 30 December 2019, 国防工业出版社 * |
| HUANHUAN LIU等: "Remarkably enhanced activity of 4A zeolite modified Pt/reduced graphene oxide electrocatalyst towards methanol electrooxidation in alkaline medium", 《IONICS》 * |
| 赵晓婵等: "分子筛 /石墨烯复合电极材料电化学性能的对比研究", 《盐湖研究》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113908830A (en) * | 2021-09-23 | 2022-01-11 | 西安交通大学 | Supported noble metal catalyst, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112717980B (en) | 2023-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhong et al. | Bismuth nanodendrites as a high performance electrocatalyst for selective conversion of CO 2 to formate | |
| EP2959970B1 (en) | Carbon material for catalyst support use | |
| Shi et al. | FeNi-functionalized 3D N, P doped graphene foam as a noble metal-free bifunctional electrocatalyst for direct methanol fuel cells | |
| JP5557564B2 (en) | Nitrogen-containing carbon alloy and carbon catalyst using the same | |
| CN110067003B (en) | Metal monoatomic doped graphene material and preparation method and application thereof | |
| CN110767914B (en) | Co-N doped porous carbon-coated carbon nanotube core-shell structure catalyst and preparation method and application thereof | |
| CN110961162B (en) | Catalyst carrier, precious metal catalyst, and preparation method and application thereof | |
| CN113437314B (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| CN108315758B (en) | Catalyst for producing hydrogen by electrolyzing water and preparation method thereof | |
| CN113270597B (en) | C 3 N 4 Coated carbon nano tube loaded NiFe dual-functional oxygen electrocatalyst and preparation method thereof | |
| Divya et al. | Platinum–graphene hybrid nanostructure as anode and cathode electrocatalysts in proton exchange membrane fuel cells | |
| CN112820886B (en) | Three-dimensional hierarchical porous nonmetal carbon-based material, and preparation method and application thereof | |
| CN111659394A (en) | Copper-based catalyst and preparation method and application thereof | |
| CN114300693A (en) | Method for improving stability of fuel cell carbon-supported platinum-based catalyst through activation of carbon carrier | |
| CN111342070A (en) | High-performance low-Pt-loading fuel cell oxygen reduction catalyst and preparation method thereof | |
| CN113611874A (en) | Composite carbon carrier alloy catalyst and preparation method and application thereof | |
| CN118547328A (en) | Catalyst for PEM water electrolysis, preparation method and application thereof | |
| CN114335572B (en) | Metal oxide composite carbon-supported platinum-based catalyst for fuel cell and preparation method thereof | |
| CN111729680A (en) | High-efficiency bifunctional oxygen electrocatalyst with heterostructure and preparation and application thereof | |
| CN113718269B (en) | Electrocatalytic material and preparation method and application thereof | |
| CN111129510A (en) | Preparation method and application of carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst | |
| Zou et al. | Three-dimensional nano-framework CoP/Co 2 P/Co 3 O 4 heterojunction as a trifunctional electrocatalyst for metal–air battery and water splitting | |
| CN112657523A (en) | Preparation method of molybdenum disulfide nanosheet/carbon nitride nanosheet/graphene three-dimensional composite electrode catalyst | |
| CN112717980B (en) | Composite catalyst and preparation method and application thereof | |
| CN113638007A (en) | Hydrogen electrolysis catalyst and preparation method 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 |