CN112803031A - Porous carbon-based catalyst based on hollow ZSM-5 and preparation method thereof - Google Patents
Porous carbon-based catalyst based on hollow ZSM-5 and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 43
- -1 platinum ion Chemical class 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 27
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 26
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 26
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 23
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 12
- 238000012986 modification Methods 0.000 abstract description 12
- 238000005342 ion exchange Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 61
- 238000005406 washing Methods 0.000 description 22
- 238000001035 drying Methods 0.000 description 19
- 238000001027 hydrothermal synthesis Methods 0.000 description 16
- 239000002808 molecular sieve Substances 0.000 description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000013354 porous framework Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8867—Vapour deposition
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- 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 provides a preparation method of a porous carbon-based catalyst based on hollow ZSM-5, which comprises the following steps: sequentially mixing the hollow ZSM-5 with an ammonium ion-containing solution and a calcium ion-containing solution, and modifying to obtain modified hollow ZSM-5; mixing the modified hollow ZSM-5 with a platinum ion-containing solution, and impregnating to obtain hollow ZSM-5 loaded platinum; performing chemical vapor deposition on the hollow ZSM-5 supported platinum by using a hydrocarbon as a carbon source to obtain a hollow ZSM-5 supported platinum-carbon material; and mixing the hollow ZSM-5 supported platinum-carbon material with alkali liquor, and etching to obtain the porous carbon-based catalyst. The porous carbon-based catalyst prepared by combining ion exchange modification, a wet chemical impregnation method and chemical vapor deposition has the advantages of high specific surface area, hierarchical porous structure and high stability.
Description
Technical Field
The invention belongs to the technical field of carbon-based electro-catalysts, and particularly relates to a porous carbon-based catalyst based on hollow ZSM-5 and a preparation method thereof.
Background
Porous carbon-based materials are widely used in electrochemical catalysis due to their high specific surface area, e.g., as a support due to their large surface area, as a catalyst due to their adjustable active sites and high electrical conductivity. In particular, porous carbon-based catalysts exhibit favorable properties in reactions involved in next-generation energy devices, such as Oxygen Reduction Reaction (ORR), Methanol Oxidation Reaction (MOR), and Formic Acid Oxidation Reaction (FAOR). In this regard, porous carbon-based materials have attracted extensive research interest, particularly platinum (Pt) -based porous carbon catalysts, which have the advantages of unique pore structure, large surface area, excellent structural stability and high conductivity, and are excellent in electrochemical catalysis, because the porous framework not only increases the active molecules in the accessible region of the reactant, but also improves electron mobility and provides efficient mass transfer in the catalytic reaction. But its catalytic activity decreases during the operation of the fuel cell for the following reasons: (1) carbon support corrosion leads to Pt loss and aggregation; (2) aggregation of Pt nanoparticles driven by surface tension; (3) ostwald ripening; (4) the potential-dependent chemical dissolution of Pt and migration into the proton exchange membrane. Therefore, there is a need for an improvement in a porous carbon-based catalyst to improve its stability to avoid the problem of a decrease in catalytic activity during use.
Disclosure of Invention
The invention aims to provide a porous carbon-based catalyst based on hollow ZSM-5 and a preparation method thereof. The porous carbon-based catalyst provided by the invention has excellent stability, can realize self-support, and can avoid the problem of reduction of catalytic activity when being used in a fuel cell.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a porous carbon-based catalyst based on hollow ZSM-5, which comprises the following steps:
(1) sequentially mixing the hollow ZSM-5 with an ammonium ion-containing solution and a calcium ion-containing solution, and modifying to obtain modified hollow ZSM-5;
(2) mixing the modified hollow ZSM-5 obtained in the step (1) with a platinum ion-containing solution, and impregnating to obtain hollow ZSM-5 supported platinum;
(3) performing chemical vapor deposition on the hollow ZSM-5 supported platinum obtained in the step (2) by using a hydrocarbon as a carbon source to obtain a hollow ZSM-5 supported platinum-carbon material;
(4) and (4) mixing the hollow ZSM-5 loaded platinum-carbon material obtained in the step (3) with alkali liquor, and etching to obtain the porous carbon-based catalyst.
Preferably, the concentration of ammonium ions in the ammonium ion-containing solution and the concentration of calcium ions in the calcium ion-containing solution in the step (1) are 0.5-2 mol/L independently.
Preferably, the platinum ion-containing solution in the step (2) is a tetraammineplatinum nitrate solution or a chloroplatinic acid solution.
Preferably, the concentration of platinum ions in the platinum ion-containing solution in the step (2) is 1-3 mmol/L.
Preferably, the ratio of the mass of the modified hollow ZSM-5 in step (2) to the volume of the platinum ion-containing solution is 0.1 g: (10-50) mL.
Preferably, the time for soaking in the step (2) is 6-24 h.
Preferably, the chemical vapor deposition in step (3) is performed in a protective atmosphere.
Preferably, the temperature of the chemical vapor deposition in the step (3) is 750-1000 ℃; the time of the chemical vapor deposition is 1-4 h.
Preferably, the alkali liquor in the step (4) is sodium hydroxide solution or ammonia water; the concentration of the alkali liquor is 1-3 mol/L.
The invention also provides the hollow ZSM-5-based porous carbon-based catalyst prepared by the preparation method in the technical scheme, wherein the porous carbon-based catalyst comprises platinum and porous carbon.
The invention provides a preparation method of a porous carbon-based catalyst based on hollow ZSM-5, which comprises the following steps: sequentially mixing the hollow ZSM-5 with an ammonium ion-containing solution and a calcium ion-containing solution, and modifying to obtain modified hollow ZSM-5; mixing the modified hollow ZSM-5 with a platinum ion-containing solution, and impregnating to obtain hollow ZSM-5 loaded platinum; performing chemical vapor deposition on the hollow ZSM-5 supported platinum by using a hydrocarbon as a carbon source to obtain a hollow ZSM-5 supported platinum-carbon material; and mixing the hollow ZSM-5 supported platinum-carbon material with alkali liquor, and etching to obtain the porous carbon-based catalyst. According to the invention, through the combination of ion exchange modification, a wet chemical impregnation method and chemical vapor deposition, ammonium ions are utilized to increase the acidity of the hollow ZSM-5 molecular sieve, dredge the pore channel of the molecular sieve, improve the pore structure of the molecular sieve, facilitate the modification of calcium ions, improve the loading capacity of platinum and improve the stability; by using the cations in the calcium ion exchange molecular sieve, calcium ions can interact with a carbon skeleton through coordination bonds during subsequent carbon deposition, so that the deposition degree of carbon during chemical vapor deposition is increased, high graphitization is realized, and the stability is further improved; and finally, etching the ZSM-5 template by adopting alkali liquor to obtain the porous carbon-based catalyst with the hierarchical porous structure, wherein the porous carbon-based catalyst is high in stability and capable of realizing self-support, and the problem that the catalytic activity of the traditional carbon-supported catalyst is reduced when the porous carbon-based catalyst is used in a fuel cell can be solved. Experimental results show that the porous carbon-based catalyst prepared by the preparation method provided by the invention can provide 100mA cm under the ultralow potential of only 245mV-2Under the current density condition of (2), the initial potential of oxygen reduction is 0.91V, and the half-wave potential is 0.75V.
Drawings
FIG. 1 is an SEM image of ZSM-5 prepared in example 1;
FIG. 2 is a TEM image of a hollow ZSM-5 prepared in example 1;
FIG. 3 is a TEM image of a porous carbon-based catalyst prepared in example 1;
FIG. 4 is a Raman diagram of a porous carbon-based catalyst prepared in example 1;
FIG. 5 is a TEM image of a porous carbon-based catalyst prepared in example 1;
fig. 6 is a graph of catalytic performance of the porous carbon-based catalyst prepared in example 1.
Detailed Description
The invention provides a preparation method of a porous carbon-based catalyst based on hollow ZSM-5, which comprises the following steps:
(1) sequentially mixing the hollow ZSM-5 with an ammonium ion-containing solution and a calcium ion-containing solution, and modifying to obtain modified hollow ZSM-5;
(2) mixing the modified hollow ZSM-5 obtained in the step (1) with a platinum ion-containing solution, and impregnating to obtain hollow ZSM-5 supported platinum;
(3) performing chemical vapor deposition on the hollow ZSM-5 supported platinum obtained in the step (2) by using a hydrocarbon as a carbon source to obtain a hollow ZSM-5 supported platinum-carbon material;
(4) and (4) mixing the hollow ZSM-5 loaded platinum-carbon material obtained in the step (3) with alkali liquor, and etching to obtain the porous carbon-based catalyst.
The invention mixes the hollow ZSM-5 with the ammonium ion-containing solution and the calcium ion-containing solution in turn to carry out modification, thus obtaining the modified hollow ZSM-5.
In the invention, ammonium ions are utilized to increase the acidity of the hollow ZSM-5 molecular sieve, dredge the pore channel of the molecular sieve, improve the pore structure of the molecular sieve, facilitate the modification of calcium ions, and not only can improve the loading capacity of platinum, but also can improve the stability; by using the cations in the calcium ion exchange molecular sieve, calcium ions can interact with a carbon skeleton through coordination bonds during subsequent carbon deposition, the deposition degree of carbon during chemical vapor deposition is increased, high graphitization is realized, and the stability is further improved.
In the invention, the preparation method of the hollow ZSM-5 is preferably to mix ZSM-5 with alkali liquor and etch the mixture to obtain the hollow ZSM-5.
In the invention, the ZSM-5 is preferably prepared by mixing tetrapropylammonium hydroxide, deionized water, sodium metaaluminate and tetraethoxysilane and carrying out hydrothermal reaction on the mixture.
In the invention, the weight ratio of the tetrapropylammonium hydroxide, the deionized water, the sodium metaaluminate and the ethyl orthosilicate is preferably (5-10): (300-600): (0.12-0.16): (5-10), more preferably (5-9): (398 to 500): (0.12-0.14): (6-8). The sources of tetrapropylammonium hydroxide, deionized water, sodium metaaluminate and ethyl orthosilicate are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the invention, when the quantity ratio of the tetrapropylammonium hydroxide, the deionized water, the sodium metaaluminate and the ethyl orthosilicate is in the range, the benzene ring-shaped ZSM-5 molecular sieve with complete morphology and structure, uniform size and uniform distribution can be obtained.
In the invention, the mixing of the tetrapropylammonium hydroxide, the deionized water, the sodium metaaluminate and the ethyl orthosilicate is preferably carried out under the condition of stirring; the mixing sequence is preferably that the tetrapropyl ammonium hydroxide and the deionized water are mixed firstly, and then the sodium metaaluminate and the ethyl orthosilicate are sequentially added.
In the invention, the mixing time of the tetrapropyl ammonium hydroxide and the deionized water is preferably 10-60 min, and more preferably 30-50 min; the time interval for sequentially adding the sodium metaaluminate and the ethyl orthosilicate is preferably 10-150 min, and more preferably 30-120 min. In the present invention, the addition of one of the starting materials at intervals is carried out in order to allow the reaction to proceed gradually and to ensure the completion of the reaction in each step, avoiding the occurrence of uncontrollable side reactions.
After the tetrapropylammonium hydroxide, the deionized water, the sodium metaaluminate and the ethyl orthosilicate are mixed, the product obtained by mixing is preferably continuously stirred for 6-12 hours. In the invention, the raw materials can be uniformly mixed by stirring after mixing.
In the present invention, the hydrothermal reaction is preferably carried out in a closed vessel; the closed container is preferably a polytetrafluoroethylene-lined high-pressure reaction kettle; the temperature of the hydrothermal reaction is preferably 100-180 ℃, and more preferably 120-150 ℃; the time of the hydrothermal reaction is preferably 12-24 hours, and more preferably 15-20 hours. The invention has no special limitation on the type of the polytetrafluoroethylene lining high-pressure reaction kettle, and the polytetrafluoroethylene lining high-pressure reaction kettle known by the technical personnel in the field can be adopted. In the present invention, the hydrothermal reaction is carried out in a density vessel, which can prevent volatilization of a solvent or an intermediate product during the reaction; the high-pressure reaction kettle with the polytetrafluoroethylene lining is adopted as the closed container, so that no adverse effect is caused on the reaction due to high temperature resistance and excellent non-adhesiveness; when the temperature of the hydrothermal reaction is in the range, enough energy can be provided for the hydrothermal reaction, and the movement collision of reactant molecules is accelerated, so that the reaction is complete; when the hydrothermal reaction time is within the above range, the reaction can be more sufficiently performed.
After the hydrothermal reaction is finished, the product obtained by the hydrothermal reaction is preferably subjected to centrifugation, washing, drying and roasting in sequence to obtain the ZSM-5.
In the invention, the speed of the centrifugation is preferably 5000-9000 rpm, and the time of the centrifugation is preferably 3-5 min. The washing operation is not particularly limited in the present invention, and a washing operation known to those skilled in the art may be used. The drying operation is not particularly limited in the present invention, and the drying operation may be carried out until the weight is constant. In the present invention, the calcination is preferably carried out in a muffle furnace; the roasting temperature is preferably 500-750 ℃, and more preferably 550-650 ℃; the roasting temperature is preferably 3-6 h, and more preferably 4-5 h. The type of the muffle furnace is not particularly limited, and the muffle furnace known to those skilled in the art can be used. In the present invention, the calcination is for removing the template.
In the invention, the alkali liquor used for preparing the hollow ZSM-5 is preferably sodium hydroxide solution; the concentration of the alkali liquor is preferably 0.02-0.5 mol/L, more preferably 0.1-0.4 mol/L, and even more preferably 0.2-0.3 mol/L. The preparation method of the alkali liquor is not particularly limited, and the alkali liquor can be prepared by adopting a preparation method well known to a person skilled in the art. In the invention, when the concentration of the alkali liquor used for preparing the hollow ZSM-5 is in the range, the multistage pore canal molecular sieve with a large amount of micropores, mesopores and a small amount of macropores can be obtained, and the zeolite structure is maintained.
In the present invention, the etching of the ZSM-5 is preferably performed under oil bath conditions; the temperature of the oil bath is preferably 50-80 ℃, and more preferably 65-70 ℃; the time for etching the ZSM-5 is preferably 30-60 min, and more preferably 45-50 min. In the invention, the ZSM-5 etching is carried out under the conditions so as to ensure that the etching is more complete.
After the ZSM-5 is etched, the invention preferably carries out centrifugation and washing on the product obtained by etching the ZSM-5 in sequence to obtain the hollow ZSM-5.
In the present invention, the operation of the centrifugation and washing is preferably the same as the operation of the centrifugation and washing of the product obtained by the hydrothermal reaction, and will not be described herein again.
In the invention, the concentration of ammonium ions in the ammonium ion-containing solution and the concentration of calcium ions in the calcium ion-containing solution are independently preferably 0.5-2 mol/L, and more preferably 1-1.5 mol/L; the solution containing ammonium ions is preferably an ammonium chloride solution; the calcium ion-containing solution is preferably a calcium nitrate solution. The preparation method of the ammonium chloride solution and the calcium nitrate solution is not particularly limited in the present invention, and the ammonium chloride solution and the calcium nitrate solution may be prepared by a preparation method known to those skilled in the art. In the present invention, the above ranges of the ammonium ion and calcium ion concentrations enable the carbon material to be deposited more favorably.
In the present invention, the mixing of the hollow ZSM-5 with the ammonium ion-containing solution and the calcium ion-containing solution in this order is preferably performed under oil bath conditions; the temperature of the oil bath is preferably 50-80 ℃, and more preferably 60-70 ℃; the mixing time of the hollow ZSM-5 and the ammonium ion-containing solution is preferably 6-12 h, and more preferably 8-10 h; the mixing time of the solution obtained by mixing the hollow ZSM-5 and the ammonium ion-containing solution and the calcium ion-containing solution is preferably 6-12 hours, and more preferably 8-10 hours. In the present invention, the mixing time is within the above range to allow more complete ion exchange.
After the modification of the hollow ZSM-5 is finished by adopting the ammonium ion-containing solution, the invention preferably carries out centrifugation, washing, drying and roasting on the product obtained by the modification in sequence.
In the present invention, the operations of centrifuging, washing, drying and calcining are preferably the same as the operations of centrifuging, washing, drying and calcining the product obtained by the hydrothermal reaction in sequence, and are not described herein again.
After the product obtained by roasting is modified by adopting a calcium ion-containing solution, the invention preferably carries out centrifugation, washing, drying and roasting on the modified product in sequence to obtain the modified hollow ZSM-5.
In the present invention, the operations of centrifuging, washing, drying and calcining are preferably the same as the operations of centrifuging, washing, drying and calcining the product obtained by the hydrothermal reaction in sequence, and are not described herein again.
After the modified hollow ZSM-5 is obtained, the modified hollow ZSM-5 is mixed with a platinum ion-containing solution and impregnated to obtain the hollow ZSM-5 supported platinum.
In the present invention, the platinum ion-containing solution is preferably a tetraamineplatinum nitrate solution or a chloroplatinic acid solution; the concentration of platinum ions in the platinum ion-containing solution is preferably 1 to 3mmol/L, and more preferably 1.5 to 2.5 mmol/L. The preparation method of the tetraammineplatinum nitrate solution or chloroplatinic acid solution is not particularly limited in the present invention, and the solution may be prepared by a preparation method known to those skilled in the art.
In the present invention, the ratio of the mass of the modified hollow ZSM-5 to the volume of the platinum ion-containing solution is preferably 0.1 g: (10-50) mL, more preferably 0.1 g: (20-40) mL, more preferably 0.1 g: (30-35) mL; the soaking time is preferably 6-24 h, more preferably 10-20 h, and even more preferably 12-18 h. In the present invention, the temperature for the impregnation is not particularly limited, and the impregnation may be performed at room temperature. In the present invention, the Pt metal loading and dispersion can be maximally ensured when the ratio of the mass of the modified hollow ZSM-5 to the volume of the platinum ion-containing solution and the impregnation time are within the above ranges.
After the impregnation is finished, the invention preferably sequentially centrifuges, washes and dries the impregnated product to obtain the hollow ZSM-5 supported platinum.
In the present invention, the operations of centrifuging, washing and drying are preferably the same as the operations of sequentially centrifuging, washing and drying the product obtained by the hydrothermal reaction, and are not described herein again.
After the hollow ZSM-5 supported platinum is obtained, the invention takes hydrocarbon as a carbon source to carry out chemical vapor deposition on the hollow ZSM-5 supported platinum to obtain the hollow ZSM-5 supported platinum-carbon material.
In the present invention, the hydrocarbon is preferably at least one of methane, ethylene and acetylene, and more preferably methane; the flow rate of the hydrocarbon is preferably 20-100 cc, and more preferably 40-80 cc. In the invention, when the hydrocarbon is methane, the molecule of the hydrocarbon is small, which is beneficial to carbon deposition; when the flow rate of the hydrocarbon is within the range, the carbon material monomer with complete shape and structure, uniform size and uniform distribution can be obtained.
In the present invention, the chemical vapor deposition is preferably carried out in a protective atmosphere; the protective atmosphere is preferably an inert gas, more preferably argon or nitrogen; the flow rate of the protective atmosphere is preferably 100-300 cc, and more preferably 150-200 cc; the temperature of the chemical vapor deposition is preferably 750-1000 ℃, more preferably 800-950 ℃, and more preferably 850-900 ℃; the time of the chemical vapor deposition is preferably 1-4 hours, and more preferably 2-3 hours. In the present invention, the temperature and time of the chemical vapor deposition are within the above ranges to allow sufficient completion of carbon deposition and achieve high graphitization.
After the hollow ZSM-5 supported platinum-carbon material is obtained, the hollow ZSM-5 supported platinum-carbon material is mixed with alkali liquor and etched to obtain the porous carbon-based catalyst.
In the invention, the alkali solution mixed with the hollow ZSM-5 supported platinum-carbon material is preferably sodium hydroxide solution or ammonia water; the concentration of the alkali liquor mixed with the hollow ZSM-5 loaded platinum-carbon material is preferably 1-3 mol/L, and more preferably 2 mol/L. The preparation method of the alkali liquor is not particularly limited in the invention, and the alkali liquor can be prepared by adopting a preparation method well known to those skilled in the art. The dosage of the alkali liquor is not specially limited, and can be adjusted according to actual conditions. The time and temperature of the etching are not particularly limited, and the ZSM-5 template can be removed. In the present invention, the concentration of the alkali solution mixed with the hollow ZSM-5 supported platinum-carbon material is within the above range, and the ZSM-5 template can be removed by the high concentration alkali solution.
After the etching is finished, the invention preferably carries out centrifugation, washing and drying on the product obtained by the etching in sequence to obtain the porous carbon-based catalyst.
In the invention, the speed of centrifugation is preferably 9000-12000 rpm, more preferably 10000-11000 rpm; the time for centrifugation is preferably 3-5 min. In the invention, when the centrifugation speed is in the range, the separation of the porous carbon-based catalyst and the ZSM-5 molecular sieve can be ensured, the porous carbon-based catalyst is ensured to be completely attached to the centrifugal tube, and the collection is facilitated.
In the present invention, the washing operation is the same as the washing operation of the product obtained by the hydrothermal reaction, and is not described herein again.
In the present invention, the drying is preferably freeze-drying; the drying is preferably carried out in a freeze dryer; the drying time is preferably 12-24 h. The type of the freeze dryer is not particularly limited in the present invention, and a freeze dryer known to those skilled in the art may be used.
According to the invention, through the combination of ion exchange modification, a wet chemical impregnation method and chemical vapor deposition, ammonium ions are utilized to increase the acidity of the hollow ZSM-5 molecular sieve, dredge the pore channel of the molecular sieve, improve the pore structure of the molecular sieve, facilitate the modification of calcium ions, improve the loading capacity of platinum and improve the stability; by using the cations in the calcium ion exchange molecular sieve, calcium ions can interact with a carbon skeleton through coordination bonds during subsequent carbon deposition, so that the deposition degree of carbon during chemical vapor deposition is increased, high graphitization is realized, and the stability is further improved; and finally, etching the ZSM-5 template by adopting alkali liquor to obtain the porous carbon-based catalyst with the hierarchical porous structure, wherein the porous carbon-based catalyst is high in stability and capable of realizing self-support, and the problem that the catalytic activity of the traditional carbon-supported catalyst is reduced when the porous carbon-based catalyst is used in a fuel cell can be solved.
According to the invention, through the combination of hydrothermal reaction, wet chemical impregnation and chemical vapor deposition, the simple preparation of the porous carbon-based catalyst is realized, the reaction time is short, the raw material cost is lower, the method is suitable for industrial scale production, the prepared catalyst has a high specific surface area, and has a hierarchical porous structure, and a series of excellent characteristics such as acid and alkali resistance, corrosion resistance, high temperature resistance, low temperature resistance, high catalytic activity, stability and the like.
The invention also provides the hollow ZSM-5-based porous carbon-based catalyst prepared by the preparation method in the technical scheme, wherein the porous carbon-based catalyst comprises platinum and porous carbon.
The porous carbon-based catalyst provided by the invention is an in-situ supported Pt porous carbon nano structure based on hollow ZSM-5, has the advantages of unique pore structure, high specific surface area, excellent structural stability, high conductivity and the like, has excellent performance in electrochemical catalysis, and the porous framework not only can increase active molecules in a reactant accessible region, but also can improve the electron mobility and provide effective mass transfer in catalytic reaction.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Mixing 12g of tetrapropyl ammonium hydroxide and 47g of deionized water, and stirring for 30 min; then adding 0.07g of sodium metaaluminate, and stirring for 2 hours; finally, 8.3g of ethyl orthosilicate is added, the mixture is sealed and stirred for 12 hours at room temperature to obtain a mixed solution; the weight ratio of the tetrapropylammonium hydroxide to the deionized water to the sodium metaaluminate to the ethyl orthosilicate is 9: 398: 0.12: 6;
2) transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for 24h at 150 ℃, centrifuging for 3min at 9000rpm to obtain a precipitate, washing for three times, drying in a 100 ℃ oven for 12h, then placing in a muffle furnace, and roasting at 550 ℃ for 4h to obtain ZSM-5;
3) etching ZSM-5 with 0.2mol/L sodium hydroxide solution for 30min under the condition of oil bath at 65 ℃, centrifugally washing for three times, and then placing in a 100 ℃ oven for drying for 12h to obtain hollow ZSM-5;
4) under the reflux condition, sequentially carrying out ion exchange modification on hollow ZSM-5 for 12 hours under the condition of 60 ℃ oil bath by using 1mol/L ammonium chloride solution and 1mol/L calcium nitrate solution, sequentially centrifugally washing precipitates for three times, then placing the precipitates in a 100 ℃ drying oven for drying for 12 hours, then placing the precipitates in a muffle furnace, and roasting the precipitates for 4 hours at 550 ℃ to obtain modified hollow ZSM-5;
5) taking 0.05g of modified hollow ZSM-5 and 20mL of tetrammine platinum nitrate solution to carry out Pt metal loading for 12h at room temperature by a wet chemical impregnation method; the concentration of platinum ions in the tetrammine platinum nitrate solution is 1.5 mmol/L; and then, carrying out centrifugal washing for three times, and then placing the materials in a freeze dryer for drying for 12 hours to obtain hollow ZSM-5 supported platinum, wherein the ratio of the mass of the modified hollow ZSM-5 to the volume of the tetrammine platinum nitrate solution is 0.1 g: 40 mL;
6) performing chemical vapor deposition on hollow ZSM-5 loaded platinum in an argon protective atmosphere by taking methane as a carbon source, setting the flow rate of methane gas to be 40cc, setting the flow rate of argon gas to be 200cc, setting the reaction temperature to be 900 ℃, and reacting for 2 hours to obtain a hollow ZSM-5 loaded platinum-carbon material;
7) and (2) etching the hollow ZSM-5 loaded platinum-carbon material by using 3mol/L sodium hydroxide solution to remove the ZSM-5 template, then centrifuging for 5min at 10000rpm to obtain a precipitate, washing for three times, and then placing in a freeze dryer for drying for 12h to obtain the porous carbon-based catalyst.
The SEM image of the ZSM-5 prepared in example 1 is shown in FIG. 1. As can be seen from FIG. 1, ZSM-5 prepared in example 1 has a benzene ring shape, a uniform size of about 0.57 μm by 1 μm, and each ZSM-5 monomer is independently dispersed.
A TEM image of the hollow ZSM-5 prepared in example 1 is shown in fig. 2. As can be seen from FIG. 2, the hollow ZSM-5 is capable of maintaining a benzene ring morphology.
A TEM image of the porous carbon-based catalyst prepared in example 1 is shown in fig. 3. As can be seen from FIG. 3, the carbon skeleton of the porous carbon-based catalyst remains intact, inherits the form of the ZSM-5 skeleton, and is independent in dispersion and uniform in size.
A raman chart of the porous carbon-based catalyst prepared in example 1 is shown in fig. 4. As can be seen from FIG. 4, due to the Si-O-Si bending vibration, it is marked v2The bands of (A) belong to the zeolite framework and the remaining bands are from the adsorbed TPA+A cation; the detailed distribution is shown in table 1.
TABLE 1 Raman Spectroscopy of porous carbon-based catalysts
| Mode(s) | ZSM-5/cm-1 | Dispensing |
| ν1 | 309 | TPA+Deformation of the cationic skeleton |
| ν2 | 381 | Delta (Si-O-Si)5MR bend |
| ν3 | 1037 | νas(C-C) stretching |
| ν4 | 1102 | CH2Vibration |
| ν5 | 1456 | HCH deformation |
| ν6 | 2883 | V (C-C) drawing |
| ν7 | 2936 | V (C-C) drawing |
| ν8 | 2980 | V (C-C) drawing |
A TEM image of the porous carbon-based catalyst prepared in example 1 is shown in fig. 5, wherein a right image of fig. 5 is a partially enlarged view of one porous carbon-based catalyst in a left image, that is, a right image is an enlarged view of a circled portion of the left image. As can be seen from fig. 5, the porous carbon-based catalyst morphology remained intact and Pt particles (right circle) were clearly visible, indicating that Pt had been successfully supported on the hollow carbon material.
The catalytic performance curve of the porous carbon-based catalyst prepared in example 1 is shown in fig. 6. As can be seen from FIG. 6, the porous carbon-based catalyst provides 100mA cm at ultra low potentials of only 245mV-2The initial potential of oxygen reduction was 0.91V and the half-wave potential was 0.75V under the current density conditions of (a), indicating that the porous carbon-based catalyst prepared in example 1 has high stability.
As can be seen from the above examples, the porous carbon-based catalyst provided by the present invention has excellent stability, can realize self-support, and can avoid the problem of reduction of catalytic activity when used in a fuel cell.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a porous carbon-based catalyst based on hollow ZSM-5 comprises the following steps:
(1) sequentially mixing the hollow ZSM-5 with an ammonium ion-containing solution and a calcium ion-containing solution, and modifying to obtain modified hollow ZSM-5;
(2) mixing the modified hollow ZSM-5 obtained in the step (1) with a platinum ion-containing solution, and impregnating to obtain hollow ZSM-5 supported platinum;
(3) performing chemical vapor deposition on the hollow ZSM-5 supported platinum obtained in the step (2) by using a hydrocarbon as a carbon source to obtain a hollow ZSM-5 supported platinum-carbon material;
(4) and (4) mixing the hollow ZSM-5 loaded platinum-carbon material obtained in the step (3) with alkali liquor, and etching to obtain the porous carbon-based catalyst.
2. The method according to claim 1, wherein the concentrations of ammonium ions in the ammonium ion-containing solution and calcium ions in the calcium ion-containing solution in step (1) are independently 0.5 to 2 mol/L.
3. The method according to claim 1, wherein the platinum ion-containing solution in the step (2) is a tetraammineplatinum nitrate solution or a chloroplatinic acid solution.
4. The preparation method according to claim 1 or 3, wherein the concentration of platinum ions in the platinum ion-containing solution in the step (2) is 1 to 3 mmol/L.
5. The method according to claim 4, wherein the ratio of the mass of the modified hollow ZSM-5 to the volume of the platinum ion-containing solution in step (2) is 0.1 g: (10-50) mL.
6. The preparation method according to claim 1, wherein the time for the impregnation in the step (2) is 6 to 24 hours.
7. The production method according to claim 1, wherein the chemical vapor deposition in the step (3) is performed in a protective atmosphere.
8. The method according to claim 1 or 7, wherein the temperature of the chemical vapor deposition in the step (3) is 750 to 1000 ℃; the time of the chemical vapor deposition is 1-4 h.
9. The preparation method according to claim 1, wherein the alkali solution in the step (4) is sodium hydroxide solution or ammonia water; the concentration of the alkali liquor is 1-3 mol/L.
10. The hollow ZSM-5 based porous carbon-based catalyst prepared by the preparation method of any one of claims 1 to 9, wherein the porous carbon-based catalyst comprises platinum and porous carbon.
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