CN112717980B - Composite catalyst and preparation method and application thereof - Google Patents
Composite catalyst and preparation method and application thereof Download PDFInfo
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- CN112717980B CN112717980B CN202011622970.7A CN202011622970A CN112717980B CN 112717980 B CN112717980 B CN 112717980B CN 202011622970 A CN202011622970 A CN 202011622970A CN 112717980 B CN112717980 B CN 112717980B
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- 239000002131 composite material Substances 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000002808 molecular sieve Substances 0.000 claims abstract description 63
- 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 63
- 229910001868 water Inorganic materials 0.000 claims abstract description 59
- 239000000725 suspension Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 14
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
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- 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
- 239000010457 zeolite Substances 0.000 claims description 13
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- 239000005457 ice water Substances 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
- 239000006185 dispersion Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000010981 drying operation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 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 4
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052680 mordenite Inorganic materials 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
- 230000035484 reaction time Effects 0.000 claims description 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 72
- 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 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 20
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 239000010411 electrocatalyst Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 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
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- 230000010287 polarization Effects 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
- 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
- 238000003483 aging Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
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- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 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
- 238000002441 X-ray diffraction 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
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 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
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- 239000002803 fossil fuel Substances 0.000 description 1
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- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- 238000004502 linear sweep voltammetry Methods 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 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
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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
-
- B01J35/33—
-
- 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
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 a suspension containing graphene oxide and a Y-type molecular sieve, and carrying out a reduction reaction under the condition of inert atmosphere to obtain a reduced graphene oxide-Y-type molecular sieve composite material, namely an rGO-Y composite material; (2) In water, the rGO-Y composite material is dispersed to obtain rGO-Y composite material suspension, and the rGO-Y composite material suspension and H 2 PtCl 6 Mixing to obtain a mixed material A; and (3) reacting the mixed material A with a reducing agent. The composite catalyst prepared by the invention has stable structure, good dispersibility, difficult occurrence of agglomeration phenomenon and good conductivity; the catalyst platinum is loaded in a small amount 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 of water electrolysis.
Description
Technical Field
The invention relates to a composite catalyst, a preparation method and application thereof.
Background
The development of chemicals based on clean energy and sustainable green raw materials is of great importance in alleviating the problems of environmental pollution and climate change caused by the use of fossil fuels. One promising strategy is to convert atmospheric water, carbon dioxide and nitrogen, etc. raw materials into important fuels or chemicals (including hydrogen, hydrocarbons, oxygenates, ammonia, etc.) by coupling renewable energy sources (solar, wind, etc.) to electrochemical processes. In recent years, the cathodic process of water splitting (HER process) has attracted a great deal of attention as a sustainable source of clean energy-hydrogen. The product of the water electrolysis hydrogen production process 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.
Currently, platinum-group noble metals (Pt, ru, pd, lr, etc.) are considered to be the best electrocatalyst for cathode hydrogen production at their low overpotential and high current density. However, the low natural reserves of noble metals have limited their widespread use in electrolyzed water due to the high cost associated with them. The addition of the electrocatalyst carrier can not only improve the utilization rate of platinum and reduce the cost, but also improve the catalyst activity. The size, dispersion and utilization efficiency of Pt nanoparticles in electrocatalysts strongly depend on the catalyst support used and its surface properties. The ideal electrocatalyst support needs to meet the following conditions: (1) higher conductivity; (2) Can be firmly connected with the active component of the catalyst, and cannot fall off; (3) a relatively high specific surface area; (4) has a certain porous structure; (5) has excellent corrosion resistance.
Carbon is used as a catalyst carrier in a quite wide range of applications, including Vulcan XC-72R carbon black (VC), carbon Nanotubes (CNTs), graphene (GE), carbon Nanofibers (CNFs), etc., wherein VC is most commonly used in commerce, and currently commonly used carrier carbon black generally has a higher specific surface area and better conductivity, and is low in cost and easy to obtain. However, carbon black particles also have some unavoidable problems when used as a carrier, and conductive carbon black is generally too small in pores to accommodate platinum particles, so that the platinum particles are substantially adhered to the surface of the conductive carbon black; conventional carbon supported metal catalysts have poor stability and typically require high metal loadings to compensate for activity losses during long run times.
Graphene is a carbon material with a honeycomb-shaped special structure, and has a theoretical specific surface area (2630 m 2 The/g) and conductivity (7200S/m) are much higher than other carbon materials. The two-dimensional structure of graphene is beneficial to the uniform distribution of platinum active components, and the capability of rapidly transferring electrons can be used for improving the reaction speed of the electrode. However, the two-dimensional structure of graphene still has limitations in the catalytic process, the graphene with 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, irreversible aggregation is easy to generate, and the specific surface area and specific capacity of the graphene are reduced.
Molecular sieves are very widely used catalysts and catalyst carrier materials, and nano particles with different catalytic capacities can be composited on the surface or in an open framework of the molecular sieves through an ion exchange method, a coprecipitation method, an impregnation method and the like. The molecular sieve microporous framework has larger specific surface area, and is favorable for uniform loading of active catalyst nano particles. However, molecular sieves have poor electrical conductivity and are not suitable as carriers for electrocatalysts directly.
Therefore, the development of a polymer with stable structure, good dispersibility, difficult occurrence of agglomeration and good conductivity is needed in the field; with a smaller amount of supported platinum, a composite catalyst exhibiting good catalytic performance.
Disclosure of Invention
The invention aims to solve the technical problems that the composite catalyst in the prior art has poor stability and dispersibility, is easy to agglomerate and has poor conductivity; the catalyst has the defects of low utilization rate, non-ideal catalytic performance and the like, and provides a composite catalyst and a preparation method and application thereof. The composite catalyst prepared by the invention has stable structure, good dispersibility, difficult occurrence of agglomeration phenomenon and good conductivity; the catalyst platinum is loaded in a small amount 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 of water electrolysis.
The invention solves the technical problems through the following technical proposal.
The invention provides a preparation method of a composite catalyst, which specifically comprises the following steps:
(1) Drying a suspension containing graphene oxide and a Y-type molecular sieve, and carrying out a reduction reaction under the condition of inert atmosphere to obtain a reduced graphene oxide-Y-type molecular sieve composite material, namely an rGO-Y composite material;
(2) In water, the rGO-Y composite material is dispersed to obtain rGO-Y composite material suspension, and the rGO-Y composite material suspension is mixed with H 2 PtCl 6 Mixing to obtain a mixed material A; and (3) reacting the mixed material A with a reducing agent.
In 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, preferably a modified Hummers method, and specifically includes the following steps: h 2 SO 4 、H 3 PO 4 、KMnO 4 Mixing graphite with 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 H 2 O 2 Mixing the water solution for the second time, standing, centrifugally collecting filter residues, and cleaning the filter residues to be neutral. The improved Hummers method is adopted in the preparation method of the graphene oxide, so that defects on the surface of the graphene can be reduced, the yield is improved, and the release of toxic gas is avoided.
Wherein the graphite may be graphite conventionally used in the art, preferably flake graphite.
The stirring time may be a time which is conventional in the art, and may be generally 10 to 15 hours, preferably 12 to 15 hours.
The stirring operation may further include a cooling operation, and generally cooling to room temperature.
Wherein, the ice water can be a two-phase mixture formed by mixing liquid water and solid water which are conventionally considered by a person skilled in the art.
Wherein the mass ratio of the ice water to the graphite may be conventional in the art, preferably (350 to 450): 1, more preferably 400:1.
wherein the H is 2 O 2 H in aqueous solution 2 O 2 The mass percentage of (c) may be conventional in the art and may be generally 20 to 35%, preferably 30 to 35%.
Wherein the graphite and the H 2 O 2 H in aqueous solution 2 O 2 The mass ratio of (2) may be conventional in the art, and may be generally (0.26 to 0.45): 1, preferably (0.30 to 0.45): 1.
the standing time can be the time which is conventional in the operation in the field, and is generally sufficient to completely separate the solid phase and the liquid phase in the system, preferably 10-15 h, more preferably 12-15 h.
Wherein the conditions and methods of cleaning may be those conventional in the art for such procedures and generally comprise the steps of: washing the filter residue to be neutral by using absolute ethyl alcohol, HCl with the mass percentage of 30% and deionized water respectively.
Wherein the cleaning operation may be followed by a drying operation. The conditions and methods of drying may be those conventional in the art, and may generally be carried out in a vacuum oven. The drying temperature may be a temperature conventional in the art for such operations, preferably 50-60 ℃.
In the step (1), the Y-type molecular sieve may be a molecular sieve in which the molar ratio of silicon element to aluminum element is (1.5 to 3) conventionally considered by those skilled in the art: 1, FAU structure molecular sieve.
In the step (1), the preparation method of the Y-type molecular sieve can be a conventional method in the field, preferably a NaOH melt-hydrothermal method, and more preferably comprises the following steps: and (3) melting the mixture of the natural zeolite and NaOH, mixing with water, aging and crystallizing.
Wherein the natural zeolite may be clinoptilolite and/or clinoptilolite as conventionally used in the art. Compared with the conventional preparation of the Y-type molecular sieve by taking silica sol and activated alumina as raw materials in the field, the preparation of the Y-type molecular sieve by taking the natural zeolite as the raw material has the advantages of low cost and simple preparation process.
Wherein the molar ratio of silicon element to aluminum element in the natural zeolite may be conventional in the art, and is preferably (4.5 to 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 conditions and methods of melting can be those conventional in the art, and generally can be used to melt the framework structure of the natural zeolite.
Wherein the melting temperature may be conventional in the art for such operations, preferably 500-650 ℃, more preferably 550-600 ℃.
Wherein the melting time may be a time conventional in this type of operation in the art, preferably 1.5 to 2.5 hours, more preferably 2 to 2.5 hours.
Wherein the mass ratio of the melted material to the water can be conventional in the art, preferably 1: (4-5), more preferably 1: (4.5-5).
The aging time may be a time conventional in this type of operation in the art, and is preferably 10 to 14 hours, more preferably 12 to 14 hours.
The crystallization temperature may be a temperature which is conventional in the art for such operations, preferably 90 to 110 ℃, more preferably 100 to 110 ℃.
The crystallization time may be a time conventional in this type of operation in the art, and is preferably 6 to 10 hours, more preferably 8 to 10 hours.
Wherein, the crystallization operation can be further followed by washing and/or drying operation. The drying temperature may be conventional in the art for such operations, and is preferably 140-160 ℃. The drying time may be a time conventional in this type of operation in the art, preferably 1.5 to 2.5 hours, more preferably 2 to 2.5 hours.
In step (1), the mass ratio of the graphene oxide to the Y-type molecular sieve may be conventional in the art, preferably 1: (4-6), more preferably 1: (4.5-5).
In the step (1), the concentration of the graphene oxide in the suspension containing the graphene oxide and the Y-type molecular sieve may be conventional in the art, preferably 4-6 mg/mL, and more preferably 5mg/mL. As is conventional in the art, the substances distributed in the liquid material are not dissolved, but merely dispersed therein in a mixture, which is referred to as a suspension.
In the step (1), the preparation method of the suspension containing graphene oxide and the Y-type molecular sieve may be conventional in the art, and may generally include the following steps: (a) The graphene oxide is dispersed in water to obtain graphene oxide gel; (b) The Y-type molecular sieve is dispersed in the graphene oxide gel.
Wherein, in the step (a), the dispersing method can be a conventional method for operation in the field, and can be ultrasonic dispersing generally.
Wherein, in the step (a), the dispersing time can be the time which is conventional in the operation in the field, and generally, the graphene oxide can be uniformly dispersed in the water.
Wherein, in the step (b), the dispersing method can be a conventional method for operation in the field, and can be ultrasonic dispersing generally.
In the step (b), the dispersing time may be a time which is conventional in the art, and generally the Y-type molecular sieve may be dispersed uniformly in the graphene oxide gel, preferably 15 to 20min, more preferably 20min.
Wherein in step (b), the dispersing operation may further include an operation of stirring. The stirring speed may be conventional in the art, preferably 800 to 1200turns/min, more preferably 1000 to 1100turns/min. The stirring time may be a time conventional in the art for such operations, preferably 25 to 35 minutes, more preferably 30 to 35 minutes.
In step (1), the drying conditions and methods may be those conventional in the art for such operations and generally comprise the steps of: stirring at 75-85 deg.c to form paste, and drying in a 45-50 deg.c oven.
In step (1), the inert atmosphere may be an inert atmosphere conventionally used in the art, for example, nitrogen.
In the step (1), the conditions and methods of the reduction reaction may be conventional in the art, and the graphene oxide may be reduced to reduced graphene oxide.
In step (1), the temperature of the reduction reaction may be a temperature conventional in this type of reaction in the art, preferably 350 to 450 ℃, more preferably 380 to 400 ℃.
In step (1), the time for the reduction reaction may be a time conventional in the art for such reactions, preferably 1.5 to 2.5 hours, more preferably 2 to 2.5 hours.
In step (1), the reduction reaction may further include a cooling operation, which may be generally performed to room temperature.
In step (2), the mass to volume ratio of the rGO-Y composite to the water may be conventional in the art, preferably 0.4 to 0.6mg/mL, more preferably 0.5 to 0.6mg/mL.
In step (2), the rGO-Y composite material is reacted with H 2 PtCl 6 The mass ratio of the Pt element can be conventional in the art, preferably 1: (0.6 to 1), more preferably 1: (0.7-0.8).
In step (2), the reducing agent may be H which is conventionally used in the art 2 PtCl 6 Reducing agents for reduction to Pt metal, preferably NaHB 4 And/or hydrazine hydrate, more preferably NaHB 4 。
Wherein, when the reducing agent is NaBH 4 When in use, the NaBH 4 Can be prepared by NaBH according to the conventional method in the art 4 Added in the form of an aqueous solution. Wherein the NaBH 4 NaBH in aqueous solution 4 The concentration of (C) may be conventional in the art, and is preferably 0.04 to 0.06mol/L, more preferably 0.05 to 0.06mol/L.
In step (2), the molar ratio of the mass of the rGO-Y composite to the reducing agent may be conventional in the art, preferably 3 to 5g/mol, more preferably 3 to 4g/mol.
In step (2), the dispersion method may be conventional in the art, and may be generally ultrasonic dispersion.
In the step (2), the dispersing time may be conventional in the art, and generally, the rGO-Y composite material may be uniformly dispersed in the water, preferably 0.5 to 1.5 hours, and more preferably 1 hour.
In step (2), the method of mixing may be a method conventional in this type of operation in the art, and may generally be an ultrasonic dispersion method.
In step (2), the mixing time may be a time conventional in the art for such operations, preferably 35 to 45 minutes, more preferably 40 to 45 minutes.
In the step (2), the addition method of the reducing agent may be conventional in the art, and may be generally dropwise addition.
In step (2), the reaction may be at the surface and/or inside of the rGO-Y composite, H as is conventionally believed by those skilled in the art 2 PtCl 6 Reaction of reduction to Pt metal by the reducing agent.
In step (2), the reaction time may be a time conventional in the art for such reactions, preferably 6 to 8 hours.
In the step (2), the reaction may further include any one or more of centrifugation, filtration residue collection, washing and drying.
The conditions and methods of the washing may be conventional in the art, and generally, the washing may be performed using distilled water.
Wherein the drying temperature may be conventional in the art for such operations, preferably 35-45 ℃, more preferably 40-45 ℃.
The drying time may be a time conventional in the art, preferably 20 to 30 hours, more preferably 24 to 30 hours.
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 in the field of proton exchange membrane fuel cells as a cathode catalyst.
Preferably, the composite catalyst is used as a cathode catalyst in the field of preparing hydrogen by electrolyzing water through a proton exchange membrane.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: and compounding graphene oxide and a Y-type molecular sieve, and loading metal Pt to prepare the composite catalyst, wherein the composite catalyst comprises reduced graphene oxide, the Y-type molecular sieve and a Pt metal catalyst. In the research and development process, the Y-type molecular sieve is used as a filling material to be compounded between the layers of the reduced graphene oxide so as to block the stacking between the layers of the reduced graphene oxide sheets and prevent the agglomeration of the reduced graphene oxide carrier; the reduced graphene oxide is wrapped on the surface of the Y-type molecular sieve, so that the conductivity of the Y-type molecular sieve can be obviously improved, and the complementary advantages of the reduced graphene oxide and the Y-type 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 realized with 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, the 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 graph showing the polarization of LSV of the composite catalysts prepared in examples 1-2 and comparative examples 1-2;
FIG. 2 is a Tafil slope diagram 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 different sweep rates;
FIG. 4 is a CV curve of the composite catalyst prepared in example 2 at different sweep rates;
FIG. 5 is a CV curve of the composite catalyst prepared in comparative example 1 at different sweep rates;
FIG. 6 is a CV curve of the composite catalyst prepared in comparative example 2 at different sweep rates;
FIG. 7 is a graph showing the current density of the composite catalysts prepared in examples 1 to 2 and comparative examples 1 to 2 as a function of the scanning rate;
FIG. 8 is an SEM image of a 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 means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
(1) Preparation of graphene oxide using modified Hummers method
First, H 2 SO 4 、H 3 PO 4 、KMnO 4 Mixing the graphite flakes with the crystalline flake graphite according to the mass ratio of 120:13:6:1, slightly releasing heat to 35-40 ℃, heating to 50 ℃ and stirring for 12 hours, and cooling the product to room temperature; pouring ice water, and then adding 30% by mass of H 2 O 2 Aqueous solution, crystalline flake graphite and H 2 O 2 H in aqueous solution 2 O 2 The mass ratio of (3) is 0.3:1, the product was observed to convert to a deep yellow color; 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 vacuum drying at 60 ℃ to obtain graphene oxide;
(2) Preparation of Y-type molecular sieve using natural zeolite as raw material
Cloud mordenite (silicon to aluminum ratio of 5.1:1) and NaOH at a ratio of 7.5:9, uniformly mixing the materials in a nickel crucible, and melting the materials for 2 hours at 550 ℃; adding a certain amount of water (solid-liquid mass ratio is 1:4.5) into the molten product, uniformly mixing, stirring and ageing for 12 hours in a plastic beaker, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 8 hours at 100 ℃; repeatedly washing the product with deionized water during suction filtration, and drying at 150 ℃ for 2 hours;
(3) Preparation of reduced graphene oxide-Y-type molecular sieve composite material (rGO-Y composite material)
Adding 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-type molecular sieve, performing ultrasonic dispersion for 20min, and performing strong stirring for 30min to obtain a suspension containing graphene oxide and the Y-type molecular sieve; then, continuously stirring and evaporating water from a suspension containing graphene oxide and a Y-type molecular sieve at 80 ℃, and placing the obtained paste into an oven for drying at 45 ℃; finally, firing for 2 hours at 380 ℃ under the protection of nitrogen, and naturally cooling the obtained product to room temperature to obtain a reduced graphene oxide-Y molecular sieve composite material (rGO-Y composite material);
(4) Preparation of composite catalyst of rGO-Y composite material loaded with Pt
Dispersing 5mg of the rGO-Y composite material newly prepared in the step (3) in 10mL of water, performing ultrasonic dispersion for 1H, and adding 8.4mg of H 2 PtCl 6 (wherein the mass of Pt contained is 4 mg), and continuing to carry out ultrasonic treatment for 40min; then, 30mL of NaBH having a concentration of 0.05mol/L was added dropwise with stirring 4 Stirring the solution for 8 hours to fully react the solution; and finally, centrifugally separating the product, collecting filter residues, repeatedly cleaning the filter residues with distilled water, and vacuum drying the product at 40 ℃ for 24 hours to obtain the composite catalyst. The amount of platinum carried in the composite catalyst prepared in this example was analyzed by ICP, and the test result was 44%, and the scanning electron microscope chart thereof was shown in fig. 8. As shown in the XRD chart of FIG. 9, the structure of the Y-type molecular sieve is not influenced after rGO is coated in FIG. 9, and the diffraction peak of the Y-type molecular sieve covers the diffraction peak of rGO because the rGO content is low, so that the characteristic absorption peak of rGO is not observed.
Example 2
(1) Preparation of Graphene Oxide (GO) using modified Hummers method
First, H 2 SO 4 、H 3 PO 4 、KMnO 4 Mixing with crystalline flake graphite according to the mass ratio of 120:13:6:1,slightly releasing heat to 35-40 ℃, heating to 50 ℃ and stirring for 12 hours, and cooling the product to room temperature; pouring ice water, and then adding 30% by mass of H 2 O 2 Aqueous solution, crystalline flake graphite and H 2 O 2 H in aqueous solution 2 O 2 The mass ratio of (3) is 0.3:1, the product was observed to convert to a deep yellow color; 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 vacuum drying at 60 ℃ to obtain graphene oxide;
(2) Preparation of Y-type molecular sieve using natural zeolite as raw material
Clinoptilolite (silicon to aluminum ratio 5.4:1) and NaOH in a ratio of 7.5:9, uniformly mixing the materials in a nickel crucible, and melting the materials for 2 hours at 550 ℃; adding a certain amount of water (solid-liquid mass ratio is 1:4.5) into the molten product, uniformly mixing, stirring and ageing for 12 hours in a plastic beaker, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 8 hours at 100 ℃; repeatedly washing the product with deionized water during suction filtration, and drying at 150 ℃ for 2 hours;
(3) Preparation of reduced graphene oxide-Y-type molecular sieve composite material (rGO-Y composite material)
Adding dispersed graphene oxide suspension with the concentration of 5mg/mL (the mass ratio of graphene oxide to the Y-type molecular sieve is 1:4.5) into the Y-type molecular sieve, performing ultrasonic dispersion for 20min, and performing strong stirring for 30min to obtain a suspension containing graphene oxide and the Y-type molecular sieve; then, continuously stirring and evaporating water from a suspension containing graphene oxide and a Y-type molecular sieve at 80 ℃, and placing the obtained paste into an oven for drying at 45 ℃; finally, firing for 2 hours at 380 ℃ under the protection of nitrogen, and naturally cooling the obtained product to room temperature to obtain a reduced graphene oxide-Y molecular sieve composite material (rGO-Y composite material);
(4) Preparation of composite catalyst of rGO-Y composite material loaded with Pt
Dispersing 5mg of the rGO-Y composite material newly prepared in the step (3) in 10mL of water, performing ultrasonic dispersion for 1H, and adding 7.35mg of H 2 PtCl 6 (wherein the mass of Pt contained is 3.5 mg), and continuing to carry out ultrasonic treatment for 40min; then, 25mL of NaBH having a concentration of 0.05mol/L was added dropwise with stirring 4 Stirring the solution for 8 hours to fully react the solution; and finally, centrifugally separating the product, collecting filter residues, repeatedly cleaning the filter residues with distilled water, and vacuum drying the product at 40 ℃ for 24 hours to obtain the composite catalyst. The amount of platinum carried in the composite catalyst prepared in this example was analyzed by ICP, and the test result was 41%.
Comparative example 1
As a comparative example, an imported brand commercial platinum carbon catalyst was purchased with XC-72R carbon black as a support and tested for 60% platinum loading using ICP. Unlike examples 1 and 2, the amount of platinum carried was higher.
Comparative example 2
(1) Preparation of Y-type molecular sieve using natural zeolite as raw material
Cloud mordenite (silicon to aluminum ratio of 5.1:1) and NaOH at a ratio of 7.5:9, uniformly mixing the materials in a nickel crucible, and melting the materials for 2 hours at 550 ℃; adding a certain amount of water (solid-liquid mass ratio is 1:4.5) into the molten product, uniformly mixing, stirring and ageing for 12 hours in a plastic beaker, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 8 hours at 100 ℃; repeatedly washing the product with deionized water during suction filtration, and drying at 150 ℃ for 2 hours;
(2) Preparation of graphene-Y-type molecular sieve composite material (GE-Y composite material), adding dispersed Graphene (GE) dispersion liquid with concentration of 5mg/mL (the mass ratio of GE to Y-type molecular sieve is mixed) into a Y-type molecular sieve, wherein the thickness of graphene is 1-5 nm, and after ultrasonic dispersion for 20min, stirring strongly for 30min to obtain uniform suspension. Then, the suspension was continuously stirred at 80 ℃ to evaporate water, and the obtained paste was dried in an oven at 45 ℃. Finally, firing for 2 hours 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
Dispersing 5mg of the GE-Y composite material newly prepared in the step (2) in 10mL of water, performing ultrasonic dispersion for 1h, and adding 8.4. 8.4mgH 2 PtCl 6 (wherein the mass of Pt contained is 4 mg), and continuing to carry out ultrasonic treatment for 40min; then, stirring is carried out30mL of NaBH with concentration of 0.05mol/L is added dropwise 4 Stirring the solution for 8 hours to fully react the solution; and finally, centrifugally separating the product, collecting filter residues, repeatedly cleaning the filter residues with distilled water, and vacuum drying the product at 40 ℃ for 24 hours to obtain the composite catalyst.
Comparative example 3
The difference compared with example 1 is only that the material addition sequence in step (3) and step (4) is different, specifically:
step (1) and step (2) are the same as in example 1;
(3) Preparation of Y-molecular sieve-Pt composite material (Y-Pt composite material)
Dispersing 4mg of the Y-type molecular sieve newly prepared in the step (2) in 10mL of water, performing ultrasonic dispersion for 1H, and adding 8.4mg of H 2 PtCl 6 (wherein the mass of Pt contained is 4 mg), and continuing to carry out ultrasonic treatment for 40min; then, 30mL of NaBH having a concentration of 0.05mol/L was added dropwise with stirring 4 Stirring the solution for 8 hours to fully react the solution; finally, centrifugally collecting the product, 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 dispersed graphene oxide suspension with the concentration of 5mg/mL (the mass ratio of graphene oxide to Y-type molecular sieve is 1:5) into the Y-Pt composite material prepared in the step (3), performing ultrasonic dispersion for 20min, and performing strong stirring for 30min to obtain a suspension; then, continuously stirring the suspension at 80 ℃ to evaporate water, and putting the obtained paste into a baking oven to be dried at 45 ℃; finally, firing for 2 hours at 380 ℃ under the protection of nitrogen, and naturally cooling the obtained product to room temperature to obtain the composite material.
The composite material graphene prepared in the comparative example has no Pt active site, and the overpotential ([email protected]) is tested -2 geo) was 183.5mV, which is far higher than that of example 1, and the catalytic performance of the composite catalyst prepared in this comparative example was poor.
Comparative example 4
The difference compared with example 1 is only that the material addition sequence in step (3) and step (4) is different, specifically:
step (1) and step (2) are the same as in example 1;
(3) Preparation of graphene oxide-Pt composite material (GO-Pt composite material)
Dispersing 1mg of the graphene oxide newly prepared in the step (1) in 10mL of water, performing ultrasonic dispersion for 1H, and adding 8.4mg of H 2 PtCl 6 (wherein the mass of Pt contained is 4 mg), and continuing to carry out ultrasonic treatment for 40min; then, 30mL of NaBH having a concentration of 0.05mol/L was added dropwise with stirring 4 Stirring the solution for 8 hours to fully react the solution; finally, centrifugally separating the product, collecting filter residues, repeatedly cleaning the filter residues 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 for 20min, stirring for 30min with strong force to obtain a suspension of the GO-Pt composite material and the Y-type molecular sieve; then, continuously stirring and evaporating water from the suspension of the GO-Pt composite material and the Y-type molecular sieve at 80 ℃, and placing the obtained paste into a baking oven for drying at 45 ℃; finally, firing for 2 hours 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 in the comparative example is found that graphene oxide is easy to agglomerate in the preparation process, the loading amount 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 ([email protected]) of the composite material is tested -2 geo) 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 testing was performed at room temperature using an electrochemical workstation (autolab, swiss vantage). A standard three electrode system was used in the test, with a glass carbon disk electrode (diameter 5mm, loading 0.204mg cm) -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 Al 2 O 3 The working electrode was mechanically polished and then rinsed with ethanol and deionized water, respectively. Working electricityThe preparation process of the polar slurry is as follows: 2mg of the catalyst was dispersed in 500. Mu.L of a mixed solvent of water and isopropyl alcohol in a volume ratio of 4:1, and after adding 20. Mu.L of Nafion solution (5%), the mixture 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 to 2 and comparative examples 1 to 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 working electrodes prepared by the method for 30-50 times by cyclic voltammetry until signals are stable, collecting data, and calculating to obtain overpotential, tafel slope, electric double layer capacitance and cyclic performance data.
1. Test overpotential (. Eta. @10mA cm) -2 geo)
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, the smaller the energy consumption is relatively, which means that the better the electrocatalytic performance is, and the higher the catalytic activity of the composite catalyst is. For quantitative comparison of the performances of the composite catalyst, a current density of 10mA.cm was selected -2 The corresponding overpotential values are used for comparing the catalytic performances of different composite catalysts, and the results are shown in Table 1.
2. Linear Sweep Voltammetry (LSV)
The Linear Scanning Voltammetry (LSV) test is that each working electrode prepared in the step (1) is adopted, and the electrolyte is 0.5M H 2 SO 4 In the solution, the concentration of the active components is 2 mV.s -1 The scan rate of (2) was tested to obtain LSV polarization curves, the results are shown in figure 1.
The Tafel slope (Tafel slope) is obtained from the LSV polarization curve and reflects the kinetics of the electrochemical reaction. The tafel curve is obtained by redrawing an LS polarization curve (a logarithmic relation diagram of overpotential and current density), the tafel curve is shown in fig. 2, and then a 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, and the smaller the Tafel slope, the faster the current density increase, indicating that the rate-determining step is at the end of the multiple electron transfer reaction, which is typically an indicator of good electrocatalyst.
3. Electrochemically active area (ECSA)
The electrochemical activity specific surface area is one of important indexes for measuring the catalytic performance of the composite catalyst, and the electrochemical activity area is measured by an electric double layer capacitance value (C dl ) Measured by a ratio of the value to the electric double layer capacitance (C dl ) Proportional to the ratio.
C dl The test method of (2) is as follows: at different scanning speeds (10-100 mV.s -1 ) Testing, typically 5-8 consecutive scan speeds are chosen. The Cyclic Voltammetry (CV) curve obtained will gradually show a rectangle with increasing sweep rate, and in order to make the obtained data linear, an appropriate sweep rate needs to be selected. In the present embodiment, 5 different sweep rates (10, 30, 50, 70 and 90 mV.s were used in a given potential interval in order to obtain electric double layer capacitance data -1 ) Cyclic voltammetry was performed to obtain CV curves of the composite catalysts prepared in example 1, example 2, comparative example 1 and comparative example 2 at different sweep rates, respectively, as shown in fig. 3 to 6. Then, the differences (Δj=ja-jc) between the anode current density and the cathode current density corresponding to the same overpotential value (usually the intermediate value of the selected voltage range) under different sweep rates are counted respectively, the sweep rate is plotted with the difference of the current densities as the abscissa, the linear regression fit is performed on the plotted graph, the slope of the fit equation can be obtained, half of the slope is the electric double layer capacitance value, the relation curve of the current densities of the composite catalysts prepared in examples 1-2 and comparative examples 1-2 along with the change of the sweep rate is shown in fig. 7, and the electric double layer capacitance result is 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, so that the catalyst has stronger catalytic activity.
4. Cycle performance test
Working electrode made with the composite catalyst prepared in examples 1 and 2 above was measured at 2 mV.s -1 The results of the cyclic scanning for 1000 times at the scanning speed show that the polarization curve of the composite catalyst only slightly changes, and the initial voltage still remains 98%.
TABLE 1
| Composite catalyst | Overpotential ([email protected]) -2 geo) | Tafel slope | Electric double layer capacitor |
| Example 1 | 37.1mV | 27.4mV/dec | 59.98mF/cm 2 |
| Example 2 | 44.7mV | 36.7mV/dec | 55.49mF/cm 2 |
| Comparative example 1 | 48.7mV | 39.4mV/dec | 30.65mF/cm 2 |
| Comparative example 2 | 53.7mV | 40.7mV/dec | 20.6mF/cm 2 |
As can be seen from the data in table 1 and fig. 1 to 7, the overpotential and tafel slope of the catalyst were reduced and the electric double layer capacitance of the catalyst was increased as compared with the commercial catalyst. The composite of the graphene and the Y-type molecular sieve is favorable for the stable and uniform dispersion of the platinum nano particles, the utilization efficiency of platinum can be improved, and the ideal catalytic performance can be still obtained under the condition of low platinum carrying amount.
Claims (17)
1. The application of the composite catalyst as a cathode catalyst in the field of preparing hydrogen by electrolyzing water through a proton exchange membrane is characterized in that the preparation method of the composite catalyst comprises the following steps:
(1) Drying a suspension containing graphene oxide and a Y-type molecular sieve, and carrying out a reduction reaction under the condition of inert atmosphere to obtain a reduced graphene oxide-Y-type molecular sieve composite material, namely an rGO-Y composite material; the preparation method of the Y-type molecular sieve comprises the following steps: melting the mixture of natural zeolite and NaOH, mixing with water, aging, and crystallizing; the molar ratio of the silicon element to the aluminum element in the natural zeolite is (4.5-6): 1, a step of; the mass ratio of the graphene oxide to the Y-type molecular sieve is 1: (4-6); the natural zeolite is clinoptilolite and/or cloud mordenite; the mass ratio of the natural zeolite to the NaOH is 1: (1.2-1.3); the melting temperature is 500-650 ℃; the melting time is 1.5-2.5 h; the mass ratio of the melted material to the water is 1: (4-5); the aging time is 10-14 hours; the crystallization temperature is 90-110 ℃; the crystallization time is 6-10 hours; in the suspension containing the graphene oxide and the Y-type molecular sieve, the concentration of the graphene oxide is 4-6 mg/mL;
(2) In water, the rGO-Y composite material is dispersed to obtain rGO-Y composite material suspension, and the rGO-Y composite material suspension is mixed with H 2 PtCl 6 Mixing to obtain a mixed material A; the mixed material A reacts with a reducing agent to obtain the composite catalyst; the rGO-Y composite material and H 2 PtCl 6 The mass ratio of the Pt element is 1: (0.6-1).
2. The application of the composite catalyst as a cathode catalyst in the field of preparing hydrogen by electrolyzing water through a proton exchange membrane, wherein the preparation method of the graphene oxide comprises the following steps: h 2 SO 4 、H 3 PO 4 、KMnO 4 Mixing graphite with 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 H 2 O 2 Mixing the water solution for the second time, standing, centrifugally collecting filter residues, and cleaning the filter residues to be neutral.
3. The use of the composite catalyst according to claim 2 as a cathode catalyst in the field of hydrogen production by water electrolysis in proton exchange membranes, wherein the graphite is flake graphite;
or, stirring for 10-15 h;
or, the stirring operation is further followed by cooling operation;
or the mass ratio of the ice water to the graphite is (350-450): 1, a step of;
or, the H 2 O 2 H in aqueous solution 2 O 2 The mass percentage of the catalyst is 20% -35%;
or, the graphite and the H 2 O 2 H in aqueous solution 2 O 2 The mass ratio of (0.26-0.45): 1, a step of;
or standing for 10-15 h;
or, the cleaning comprises the following steps: washing the filter residue to be neutral by using absolute ethyl alcohol, HCl with the mass percentage of 30% and deionized water respectively;
or, the cleaning operation is further followed by a drying operation.
4. The application of the composite catalyst as a cathode catalyst in the field of preparing hydrogen by electrolyzing water through a proton exchange membrane, which is characterized in that the stirring time is 12-15 h;
or, the stirring operation is further followed by cooling to room temperature;
or, the mass ratio of the ice water to the graphite is 400:1, a step of;
or, the H 2 O 2 H in aqueous solution 2 O 2 The mass percentage of (2) is 30% -35%;
or, the graphite and the H 2 O 2 H in aqueous solution 2 O 2 The mass ratio of (0.30-0.45): 1, a step of;
or standing for 12-15 h.
5. The application of the composite catalyst as a cathode catalyst in the field of preparing hydrogen by electrolyzing water through a proton exchange membrane, wherein in the step (1), the melting temperature is 550-600 ℃;
or the melting time is 2-2.5 h;
or the mass ratio of the melted material to the water is 1: (4.5-5);
or, the aging time is 12-14 h;
or the crystallization temperature is 100-110 ℃;
or the crystallization time is 8-10 h;
or, the crystallization operation is further followed by a water washing and/or drying operation.
6. The use of the composite catalyst according to claim 5 as a cathode catalyst in the field of hydrogen production by water electrolysis of proton exchange membranes, wherein the drying temperature is 140-160 ℃;
or the drying time is 1.5-2.5 h.
7. The use of the composite catalyst according to claim 5 as a cathode catalyst in the field of preparing hydrogen by water electrolysis of a proton exchange membrane, wherein the drying time is 2-2.5 h.
8. Use of the composite catalyst according to claim 1 as a cathode catalyst in the field of water electrolysis in proton exchange membranes for the production of hydrogen, wherein in step (1) the drying operation comprises the steps of: stirring at 75-85 ℃ until the system becomes paste, and then placing the paste in an oven at 45-50 ℃ for drying;
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 further comprises a cooling operation.
9. The use of the composite catalyst according to claim 8 as a cathode catalyst in the field of preparing hydrogen by water electrolysis of a proton exchange membrane, 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 5mg/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 to cool to room temperature.
10. The use of the composite catalyst according to claim 1 as a cathode catalyst in the field of preparing hydrogen by water electrolysis of a proton exchange membrane, wherein in the step (1), the preparation method of the suspension containing graphene oxide and a Y-type molecular sieve comprises the following steps: (a) The graphene oxide is dispersed in water to obtain graphene oxide gel; (b) The Y-type molecular sieve is dispersed in the graphene oxide gel.
11. The use of the composite catalyst according to claim 10 as a cathode catalyst in the field of producing hydrogen by electrolysis of water through a proton exchange membrane, wherein in step (a), the dispersion method is ultrasonic dispersion;
or, in step (b), the dispersing method is ultrasonic dispersion;
or in the step (b), the dispersing time is 15-20 min;
or, in the step (b), the dispersing operation further comprises stirring operation.
12. The use of the composite catalyst according to claim 11 as a cathode catalyst in the field of producing hydrogen by electrolysis of water through a proton exchange membrane, wherein in step (b) the dispersion time is 20min;
or in the step (b), stirring operation is further included after the dispersing operation, the stirring rotation speed is 800-1200 turns/min, and the stirring time is 25-35 min.
13. The application of the composite catalyst as a cathode catalyst in the field of preparing hydrogen by electrolyzing water through a proton exchange membrane, wherein in the step (b), the dispersing operation further comprises stirring operation, and the stirring rotation speed is 1000-1100 turn/min; the stirring time is 30-35 min.
14. The application of the composite catalyst according to any one of claims 1-13 as a cathode catalyst in the field of preparing hydrogen by electrolyzing water through a proton exchange membrane, wherein in the step (2), the mass-volume ratio of the rGO-Y composite material to the water is 0.4-0.6 mg/mL;
and/or, in step (2), the rGO-Y composite is reacted with H 2 PtCl 6 The mass ratio of the Pt element is 1: (0.7 to 0.8);
and/or, in the step (2), the reducing agent is NaHB 4 And/or hydrazine hydrate；
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;
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;
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;
and/or, in the step (2), the reducing agent is added dropwise;
and/or in the step (2), the reaction time is 6-8 hours;
and/or, in the step (2), the operation of the reaction further comprises the operation of any one or more of centrifugal collection of filter residues, washing and drying.
15. The application of the composite catalyst according to any one of claims 1-13 as a cathode catalyst in the field of preparing hydrogen by electrolyzing water through a proton exchange membrane, wherein in the step (2), the mass-volume ratio of the rGO-Y composite material to the water is 0.5-0.6 mg/mL;
and/or, in the step (2), the reducing agent is NaHB 4 The NaBH 4 By NaBH 4 Adding in the form of an aqueous solution;
and/or in the step (2), the molar ratio of the mass of the rGO-Y composite material to the reducing agent is 3-4 g/mol;
and/or, in step (2), the dispersing time is 1h;
and/or, in the step (2), the mixing time is 40-45 min;
and/or, in the step (2), the operation of the reaction further comprises the operation of any one or more of centrifugal collection of filter residues, washing and drying; the washing method is that distilled water is adopted for washing; the drying temperature is 35-45 ℃; and the drying time is 20-30 hours.
16. The use of the composite catalyst as claimed in claim 15 as a cathode catalyst in the field of water electrolysis in proton exchange membranes for the production of hydrogen, wherein the NaBH 4 NaBH in aqueous solution 4 The concentration of (2) is 0.04-0.06 mol/L;
and/or, in the step (2), the operation of the reaction further comprises the operation of any one or more of centrifugal collection of filter residues, washing and drying; the washing method is that distilled water is adopted for washing; the drying temperature is 40-45 ℃; the drying time is 24-30 h.
17. The use of the composite catalyst as claimed in claim 15 as a cathode catalyst in the field of water electrolysis in proton exchange membranes for the production of hydrogen, wherein the NaBH 4 NaBH in aqueous solution 4 The concentration of (C) is 0.05-0.06 mol/L.
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