CN111068673A - Preparation method of carbon-metal oxide composite carrier and catalyst thereof - Google Patents
Preparation method of carbon-metal oxide composite carrier and catalyst thereof Download PDFInfo
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- CN111068673A CN111068673A CN202010045761.4A CN202010045761A CN111068673A CN 111068673 A CN111068673 A CN 111068673A CN 202010045761 A CN202010045761 A CN 202010045761A CN 111068673 A CN111068673 A CN 111068673A
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 58
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000003057 platinum Chemical class 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 11
- 239000000969 carrier Substances 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 238000011068 loading method Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
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- 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
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Abstract
The invention discloses a carbon-metal oxide composite carrier and a preparation method of a catalyst thereof. A preparation method of a carbon-metal oxide composite carrier comprises the following steps: (1) preparing a metal salt solution; (2) immersing a carbon carrier into the metal salt solution, adding an alcohol dispersant, performing ultrasonic treatment, and then adding alkali liquor under stirring for precipitation reaction; (3) standing, filtering, washing and drying; (4) and calcining the dried solid in an inert atmosphere to obtain the carbon-metal oxide composite carrier. The preparation method of the carbon-metal oxide composite carrier has simple preparation process and easy operation, can realize batch production, and is suitable for preparing carriers compounded by various carbon carriers and metal oxides; the catalyst prepared by the carbon-metal oxide composite carrier has good catalytic activity and good ageing resistance.
Description
Technical Field
The invention relates to the technical field of new energy materials,
in particular, the present invention relates to a carbon-metal oxide composite carrier and a method for preparing a catalyst thereof.
Background
The fuel cell is a high-efficiency power generation device which directly converts chemical energy stored in the fuel cell into electric energy which can be conveniently used through chemical reaction without conversion of other energy (heat energy and mechanical energy). Compared with other energy supplies, the energy supply system has the advantages of no pollution of products, rich fuel sources, light weight, convenience in carrying and the like, and is considered as an ideal energy utilization mode. The construction of a fuel cell is generally composed of a positive electrode material, a negative electrode material, an electrolyte, and external circuit components; among them, the catalyst constituting the cathode material is a core component of the fuel cell, and the excellence of the performance thereof directly affects the normal operation of the entire fuel cell system.
At present, a Pt/C catalyst is mainly adopted as a fuel cell catalyst, but in the using process, a pure carbon carrier inevitably corrodes at a cathode, and metal nano particles are easy to separate from the carbon carrier and gather in a large amount, so that the activity of the catalyst is reduced, and the service life of the catalyst is shortened. Designing a catalyst support with high stability is a hot spot of research in the field of polymer electrolyte fuel cells.
Compared with the traditional carbon carrier, the metal oxide carrier has strong corrosion resistance and strong bonding force with a metal catalyst, meanwhile, the addition of the oxide can improve the oxygen reduction performance of the catalyst and reduce the use of metal platinum, but the conductivity is poor, so that the defect of a single carbon carrier or a single metal oxide carrier can be overcome by researching the preparation of the composite carrier by combining carbon and the metal oxide.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the present invention aims to provide a carbon-metal oxide composite carrier and a preparation method of a catalyst thereof.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of a carbon-metal oxide composite carrier comprises the following steps:
(1) preparing a metal salt solution;
(2) immersing a carbon carrier into the metal salt solution, adding an alcohol dispersant, performing ultrasonic treatment, and then adding alkali liquor under stirring for precipitation reaction;
(3) standing, filtering, washing and drying;
(4) and calcining the dried solid in an inert atmosphere to obtain the carbon-metal oxide composite carrier.
Preferably, the metal salt solution is any one of cerium nitrate, cerium chloride, cerium carbonate, manganese nitrate, zirconium dichloride and stannous chloride, and the mass fraction of the metal salt solution is 10-20%.
Preferably, the alcohol dispersant is any one of ethanol, n-propanol and isopropanol.
Preferably, the calcination treatment temperature is 200-600 ℃, and the time is 1-3 h.
Preferably, the ultrasonic treatment time is 30-60 min.
The invention also provides the carbon-metal oxide composite carrier prepared by the preparation method, wherein the mass fraction of the metal oxide in the composite carrier is 10-30%.
The invention also provides a preparation method of the carbon-metal oxide composite carrier catalyst, which comprises the following steps:
(1) preparing a platinum salt precursor solution;
(2) immersing a carbon-metal oxide composite carrier into the platinum salt precursor solution, adding ethylene glycol, performing ultrasonic treatment at room temperature for 20-40 min, then adding alkali liquor and a reducing agent, and stirring and reacting under an inert atmosphere for 20-40 min to obtain a first mixed solution;
(3) continuously stirring and reacting the first mixed solution for 2-5 hours at the temperature of 60-90 ℃ under the inert atmosphere;
(4) solid-liquid separation, washing and drying to obtain the carbon-metal oxide composite carrier catalyst.
Preferably, the platinum salt precursor solution is chloroplatinic acid or sodium chloroplatinate.
Preferably, the alkali liquor is any one of sodium bicarbonate, sodium carbonate and sodium hydroxide.
Preferably, the drying temperature is 80-100 ℃, and the drying time is 4-8 h.
Compared with the prior art, the invention has the following technical effects:
the preparation method of the carbon-metal oxide composite carrier has simple preparation process and easy operation, can realize batch production, and is suitable for preparing carriers compounded by various carbon carriers and metal oxides; the catalyst prepared by the carbon-metal oxide composite carrier has good catalytic activity and good ageing resistance.
Drawings
FIG. 1 is a cyclic voltammogram before and after the catalyst prepared in example 1 of the present invention is used for single cell accelerated aging at 0.6-0.95V;
FIG. 2 is a cyclic voltammogram before and after the catalyst prepared in example 1 of the present invention is used for single cell 1-1.5V accelerated aging.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment 1 of the invention provides a preparation method of a carbon-metal oxide composite carrier and a catalyst thereof, which comprises the following steps:
step 1: weighing 35g of cerium nitrate salt solution with the mass fraction of 20%, 7g of carbon powder and 30mL of ethanol, placing the mixture in a beaker, and carrying out ultrasonic treatment for 30min until the mixture is uniformly dispersed;
step 2: transferring the solution to a magnetic stirrer, and dropwise adding 20mL of sodium bicarbonate solution with the mass fraction of 20% while magnetically stirring at the temperature of 25 ℃;
and step 3: magnetically stirring the mixed solution for 2 hours, carrying out suction filtration and washing on the precipitate, and then placing the carrier in an air oven for drying;
and 4, step 4: carrier to be driedGrinding, then placing in a 400 ℃ tube furnace, roasting for 2h in nitrogen atmosphere to obtain the required CeO2-a C composite carrier.
And 5: weighing 3.75g H2PtCl6Solution, 0.5g of CeO obtained above2And (3) adding 30g of ethylene glycol into the-C composite carrier, and performing ultrasonic treatment at room temperature for 30min until the dispersion is uniform.
Step 6: transferring the mixed solution after ultrasonic treatment to a three-neck flask, adding 3g of formic acid and 20g of sodium carbonate solution with the mass fraction of 15% into the solution, and stirring for 30min at room temperature under the condition of introducing nitrogen; then the temperature is increased to 80 ℃ and the reaction is continued to be stirred for 5 h.
And 7: filtering the reacted solution, washing with distilled water for several times, and drying in a drying oven at 100 ℃ for 6 hours to obtain 1g of Pt/CeO with 50% loading capacity2-a catalyst C.
Example 2
The embodiment 2 of the invention provides a preparation method of a carbon-metal oxide composite carrier and a catalyst thereof, which comprises the following steps:
step 1: weighing 15g of cerium chloride salt solution with the mass fraction of 20%, 8g of carbon powder and 30mL of n-propanol, placing in a beaker, and carrying out ultrasonic treatment for 50min until the cerium chloride salt solution is uniformly dispersed;
step 2: transferring the solution to a magnetic stirrer, and dropwise adding 20mL of sodium bicarbonate solution with the mass fraction of 20% while magnetically stirring at the temperature of 25 ℃;
and step 3: magnetically stirring the mixed solution for 1.5h, carrying out suction filtration and washing on the precipitate, and then placing the carrier in an air oven for drying;
and 4, step 4: grinding the dried carrier, then placing the carrier in a 600 ℃ tubular furnace, and roasting the carrier for 1h in the nitrogen atmosphere to obtain the required CeO2-a C composite carrier.
And 5: weighing 3.75g H2PtCl6Solution, 0.5g of CeO obtained above2And (3) adding 30g of ethylene glycol into the-C composite carrier, and performing ultrasonic treatment at room temperature for 30min until the dispersion is uniform.
Step 6: transferring the mixed solution after ultrasonic treatment to a three-neck flask, adding 3g of formic acid and 20g of sodium carbonate solution with the mass fraction of 15% into the solution, and stirring for 30min at room temperature under the condition of introducing nitrogen; then the temperature is increased to 80 ℃ and the reaction is continued to be stirred for 5 h.
And 7: filtering the reacted solution, washing with distilled water for several times, and drying in a drying oven at 100 ℃ for 6 hours to obtain 1g of Pt/CeO with 50% loading capacity2-a catalyst C.
Example 3
Embodiment 3 of the present invention provides a method for preparing a carbon-metal oxide composite carrier and a catalyst thereof, comprising the following steps:
step 1: weighing 10g of cerium chloride salt solution with the mass fraction of 20%, 8g of carbon powder and 30mL of isopropanol, placing the mixture in a beaker, and carrying out ultrasonic treatment for 40min until the mixture is uniformly dispersed;
step 2: transferring the solution to a magnetic stirrer, and dropwise adding 20mL of sodium bicarbonate solution with the mass fraction of 20% while magnetically stirring at the temperature of 25 ℃;
and step 3: magnetically stirring the mixed solution for 1h, carrying out suction filtration and washing on the precipitate, and then placing the carrier in an air oven for drying;
and 4, step 4: grinding the dried carrier, then placing the carrier in a 500 ℃ tubular furnace, and roasting the carrier for 1h in the nitrogen atmosphere to obtain the required CeO2-a C composite carrier.
And 5: weighing 3.75g H2PtCl6Solution, 0.5g of CeO obtained above2And (3) adding 30g of ethylene glycol into the-C composite carrier, and performing ultrasonic treatment at room temperature for 30min until the dispersion is uniform.
Step 6: transferring the mixed solution after ultrasonic treatment to a three-neck flask, adding 3g of formic acid and 20g of sodium carbonate solution with the mass fraction of 15% into the solution, and stirring for 30min at room temperature under the condition of introducing nitrogen; then the temperature is increased to 80 ℃ and the reaction is continued to be stirred for 5 h.
And 7: and filtering the solution after reaction, washing the solution for a plurality of times by using distilled water, and then drying the solution in a drying oven at 100 ℃ for 6 hours to obtain 1g of Pt/CeO2-C catalyst with 50% of loading capacity.
Example 4
Embodiment 4 of the present invention provides a method for preparing a carbon-metal oxide composite carrier and a catalyst thereof, including the steps of:
step 1: weighing 20g of cerium nitrate salt solution with the mass fraction of 20%, 7g of carbon powder and 30mL of ethanol, placing the mixture in a beaker, and carrying out ultrasonic treatment for 40min until the mixture is uniformly dispersed;
step 2: transferring the solution to a magnetic stirrer, and dropwise adding 20mL of sodium bicarbonate solution with the mass fraction of 20% while magnetically stirring at the temperature of 25 ℃;
and step 3: magnetically stirring the mixed solution for 2 hours, carrying out suction filtration and washing on the precipitate, and then placing the carrier in an air oven for drying;
and 4, step 4: and grinding the dried carrier, then placing the ground carrier in a 300 ℃ tubular furnace, and roasting the ground carrier for 3 hours in a nitrogen atmosphere to obtain the required composite carrier.
And 5: weighing 3.75g H2PtCl6Solution, 0.5g of CeO obtained above2And (3) adding 30g of ethylene glycol into the-C composite carrier, and performing ultrasonic treatment at room temperature for 50min until the dispersion is uniform.
Step 6: transferring the mixed solution after ultrasonic treatment to a three-neck flask, adding 3g of formic acid and 20g of sodium carbonate solution with the mass fraction of 15% into the solution, and stirring for 30min at room temperature under the condition of introducing nitrogen; then the temperature is increased to 80 ℃ and the reaction is continued to be stirred for 5 h.
And 7: filtering the reacted solution, washing with distilled water for several times, and drying in a drying oven at 100 ℃ for 6 hours to obtain 1g of Pt/CeO with 50% loading capacity2-a catalyst C.
Example 5
Embodiment 5 of the present invention provides a method for preparing a carbon-metal oxide composite carrier and a catalyst thereof, including the steps of:
step 1: weighing 30g of cerium carbonate salt solution with the mass fraction of 20%, 8g of carbon powder and 30mL of ethanol, placing the mixture in a beaker, and carrying out ultrasonic treatment for 30min until the mixture is uniformly dispersed;
step 2: transferring the solution to a magnetic stirrer, and dropwise adding 20mL of sodium bicarbonate solution with the mass fraction of 20% while magnetically stirring at the temperature of 25 ℃;
and step 3: magnetically stirring the mixed solution for 2 hours, carrying out suction filtration and washing on the precipitate, and then placing the carrier in an air oven for drying;
and 4, step 4: grinding the dried carrier, then placing the carrier in a 200 ℃ tube furnace, and roasting the carrier for 2 hours in a nitrogen atmosphere to obtain the required CeO2-a C composite carrier.
And 5: weighing 3.75g H2PtCl6Solution, 0.5g of CeO obtained above2And (3) adding 30g of ethylene glycol into the-C composite carrier, and performing ultrasonic treatment at room temperature for 40min until the dispersion is uniform.
Step 6: transferring the mixed solution after ultrasonic treatment to a three-neck flask, adding 3g of formic acid and 20g of sodium carbonate solution with the mass fraction of 15% into the solution, and stirring for 30min at room temperature under the condition of introducing nitrogen; then the temperature is increased to 80 ℃ and the reaction is continued to be stirred for 5 h.
And 7: filtering the reacted solution, washing with distilled water for several times, and drying in a drying oven at 100 ℃ for 6 hours to obtain 1g of Pt/CeO with 50% loading capacity2-a catalyst C.
Example 6
Embodiment 6 of the present invention provides a method for preparing a carbon-metal oxide composite carrier and a catalyst thereof, including the steps of:
step 1: weighing 21g of manganese nitrate salt solution with the mass fraction of 20%, 8g of carbon powder and 30mL of ethanol, placing the mixture in a beaker, and carrying out ultrasonic treatment for 50min until the mixture is uniformly dispersed;
step 2: transferring the solution to a magnetic stirrer, and dropwise adding 20mL of 20% sodium hydroxide solution while magnetically stirring at 25 ℃;
and step 3: magnetically stirring the mixed solution for 1h, carrying out suction filtration and washing on the precipitate, and then placing the carrier in an air oven for drying;
and 4, step 4: grinding the dried carrier, then placing the ground carrier in a 300 ℃ tubular furnace, and roasting the ground carrier for 2 hours in a nitrogen atmosphere to obtain the required MnO2-a C composite carrier.
And 5: weighing 3.75g H2PtCl6Solution, 0.5g MnO obtained above2And (3) adding 30g of ethylene glycol into the-C composite carrier, and performing ultrasonic treatment at room temperature for 40min until the dispersion is uniform.
Step 6: transferring the mixed solution after ultrasonic treatment to a three-neck flask, adding 3g of formic acid and 20g of sodium carbonate solution with the mass fraction of 15% into the solution, and stirring for 30min at room temperature under the condition of introducing nitrogen; then the temperature is increased to 80 ℃ and the reaction is continued to be stirred for 5 h.
And 7: filtering the reacted solution, washing with distilled water for several times, and drying in a drying oven at 100 ℃ for 6h to obtain 1g of Pt/MnO with 50% loading capacity2-a catalyst C.
Example 7
Embodiment 7 of the present invention provides a method for preparing a carbon-metal oxide composite carrier and a catalyst thereof, including the steps of:
step 1: weighing 13.5g of zirconium dichloride salt solution with the mass fraction of 20%, 8g of carbon powder and 30mL of ethanol, putting the mixture into a beaker, and carrying out ultrasonic treatment for 30min until the mixture is uniformly dispersed;
step 2: transferring the solution to a magnetic stirrer, and dropwise adding 20mL of sodium bicarbonate solution with the mass fraction of 20% while magnetically stirring at the temperature of 25 ℃;
and step 3: magnetically stirring the mixed solution for 2 hours, carrying out suction filtration and washing on the precipitate, and then placing the carrier in an air oven for drying;
and 4, step 4: grinding the dried carrier, then placing the ground carrier in a 400 ℃ tubular furnace, and roasting the ground carrier for 2 hours in a nitrogen atmosphere to obtain the required ZrO2-a C composite carrier.
And 5: weighing 3.75g H2PtCl6Solution, 0.5g of ZrO obtained above2And (3) adding 30g of ethylene glycol into the-C composite carrier, and performing ultrasonic treatment at room temperature for 40min until the dispersion is uniform.
Step 6: transferring the mixed solution after ultrasonic treatment to a three-neck flask, adding 3g of formic acid and 20g of sodium carbonate solution with the mass fraction of 15% into the solution, and stirring for 30min at room temperature under the condition of introducing nitrogen; then the temperature is increased to 80 ℃ and the reaction is continued to be stirred for 5 h.
And 7: filtering the reacted solution, washing with distilled water for several times, and drying in a drying oven at 100 ℃ for 6h to obtain 1g of Pt/ZrO with 50% loading capacity2-a catalyst C.
Example 8
Embodiment 8 of the present invention provides a method for preparing a carbon-metal oxide composite carrier and a catalyst thereof, including the steps of:
step 1: weighing 13g of stannous chloride salt solution with the mass fraction of 20%, 8g of carbon powder and 30mL of ethanol, placing the mixture in a beaker, and carrying out ultrasonic treatment for 30min until the mixture is uniformly dispersed;
step 2: transferring the solution to a magnetic stirrer, and dropwise adding 20mL of sodium bicarbonate solution with the mass fraction of 20% while magnetically stirring at the temperature of 25 ℃;
and step 3: magnetically stirring the mixed solution for 3 hours, carrying out suction filtration and washing on the precipitate, and then placing the carrier in an air oven for drying;
and 4, step 4: grinding the dried carrier, then placing the ground carrier in a 500 ℃ tubular furnace, and roasting the ground carrier for 2 hours in a nitrogen atmosphere to obtain the required SnO2-a C composite carrier.
And 5: weighing 3.75g H2PtCl6Solution, 0.5g SnO obtained as described above2And (3) adding 30g of ethylene glycol into the-C composite carrier, and performing ultrasonic treatment at room temperature for 40min until the dispersion is uniform.
Step 6: transferring the mixed solution after ultrasonic treatment to a three-neck flask, adding 3g of formic acid and 20g of sodium carbonate solution with the mass fraction of 15% into the solution, and stirring for 30min at room temperature under the condition of introducing nitrogen; then the temperature is increased to 80 ℃ and the reaction is continued to be stirred for 5 h.
And 7: filtering the reacted solution, washing with distilled water for several times, and drying in a drying oven at 100 ℃ for 6h to obtain 1g of Pt/SnO with 50% loading capacity2-a catalyst C.
The Pt loading capacity of the catalyst prepared by the embodiment of the invention is 50%, and various Pt/MO-C (M is respectively Ce, Mn, Sn and Ce) catalysts with different loading capacities of 20-50% can be prepared by adjusting the amount of the added platinum salt precursor.
The catalyst prepared by the invention can be used for preparing a Membrane Electrode Assembly (MEA) required by production, and the performance of the catalyst is evaluated through electrochemistry of a Rotating Disk Electrode (RDE) and accelerated aging experiments of monocells.
The electrochemical performance of the catalysts prepared in examples 1 to 8 of the present invention was measured using a rotating disk electrode, and the results are shown in table 1.
Table 1 statistical table of electrochemical areas of catalysts of examples 1 to 8
Application example
(1) The catalyst prepared in the embodiment 1 of the invention is sprayed to prepare a membrane electrode, and accelerated aging test is carried out, wherein the experimental conditions are as follows: the temperature of the single cell is 80 ℃, hydrogen is introduced into the anode, nitrogen is introduced into the cathode, and the relative humidity is 100%. The voltage range is 0.6V for 3s and 0.95V for 3s, 30000 circles of accelerated aging tests are carried out on the cathode surface of the electrode, and the test results are shown in figure 1. The electrochemical area is calculated, so that after 30000 cycles of accelerated aging, the electrochemical area is attenuated by 18.4%, which is within the range of 40% required by U.S. DOE and is smaller than the reported attenuation rate of the Pt/C catalyst, and the composite carrier prepared by the embodiment of the invention can improve the durability of the catalyst.
(2) The catalyst prepared in the embodiment 1 of the invention is sprayed to prepare a membrane electrode, and accelerated aging test is carried out, wherein the experimental conditions are as follows: the temperature of the single cell is 80 ℃, hydrogen is introduced into the cathode, nitrogen is introduced into the anode, and the relative humidity is 100%. The voltage range is 1-1.5Vs, 5000-turn accelerated aging tests are carried out on the anode surface of the electrode, and the test results are shown in figure 2. The electrochemical area is calculated, so that after 5000 cycles of accelerated aging, the electrochemical area is attenuated by 24.7%, which is within the range of 40% required by the U.S. DOE and is smaller than the reported attenuation rate of the Pt/C catalyst, and the composite carrier prepared by the embodiment of the invention can improve the durability of the catalyst.
The present invention is not limited to the above-described specific embodiments, and various modifications and variations are possible. Any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a carbon-metal oxide composite carrier is characterized by comprising the following steps:
(1) preparing a metal salt solution;
(2) immersing a carbon carrier into the metal salt solution, adding an alcohol dispersant, performing ultrasonic treatment, and then adding alkali liquor under stirring for precipitation reaction;
(3) standing, filtering, washing and drying;
(4) and calcining the dried solid in an inert atmosphere to obtain the carbon-metal oxide composite carrier.
2. The method for preparing a carbon-metal oxide composite carrier according to claim 1, wherein the metal salt solution is any one of cerium nitrate, cerium chloride, cerium carbonate, manganese nitrate, zirconium dichloride and stannous chloride, and the mass fraction of the metal salt solution is 10-20%.
3. The method for preparing a carbon-metal oxide composite carrier according to claim 1, wherein the alcohol dispersant is any one of ethanol, n-propanol and isopropanol.
4. The method for preparing a carbon-metal oxide composite carrier as claimed in claim 1, wherein the calcination treatment temperature is 200-600 ℃ and the time is 1-3 h.
5. The method for preparing a carbon-metal oxide composite carrier according to claim 1, wherein the ultrasonic treatment time is 30 to 60 min.
6. The carbon-metal oxide composite carrier prepared by the method for preparing a carbon-metal oxide composite carrier according to any one of claims 1 to 5, wherein the mass fraction of the metal oxide in the composite carrier is 10 to 30%.
7. A preparation method of a carbon-metal oxide composite carrier catalyst is characterized by comprising the following steps:
(1) preparing a platinum salt precursor solution;
(2) immersing a carbon-metal oxide composite carrier into the platinum salt precursor solution, adding ethylene glycol, performing ultrasonic treatment at room temperature for 20-40 min, then adding alkali liquor and a reducing agent, and stirring and reacting under an inert atmosphere for 20-40 min to obtain a first mixed solution;
(3) continuously stirring and reacting the first mixed solution for 2-5 hours at the temperature of 60-90 ℃ under the inert atmosphere;
(4) solid-liquid separation, washing and drying to obtain the carbon-metal oxide composite carrier catalyst.
8. The method of claim 7, wherein the platinum salt precursor solution is chloroplatinic acid or sodium chloroplatinate.
9. The method of claim 8, wherein the alkali solution is any one of sodium bicarbonate, sodium carbonate and sodium hydroxide.
10. The method for preparing a carbon-metal oxide composite supported catalyst according to claim 9, wherein the drying temperature is 80 to 100 ℃ and the drying time is 4 to 8 hours.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112850787A (en) * | 2021-01-27 | 2021-05-28 | 浙江高成绿能科技有限公司 | Catalyst carrier for fuel cell, catalyst and preparation method thereof |
CN113611886A (en) * | 2021-01-25 | 2021-11-05 | 南京工业大学 | Fuel cell electrocatalyst and preparation method thereof |
CN114843532A (en) * | 2022-05-09 | 2022-08-02 | 嘉庚创新实验室 | Preparation method of high-activity Pt/C catalyst |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1494304A1 (en) * | 2003-07-02 | 2005-01-05 | Nissan Motor Co., Ltd. | Electrocatalyst and method of manufacturing the same |
CN101306365A (en) * | 2008-07-03 | 2008-11-19 | 上海交通大学 | Composite anode electrocatalyst for direct methanol fuel cell |
CN109244491A (en) * | 2018-08-06 | 2019-01-18 | 浙江高成绿能科技有限公司 | A kind of fuel cell Pt/WO3The preparation method of C catalyst |
-
2020
- 2020-01-16 CN CN202010045761.4A patent/CN111068673A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1494304A1 (en) * | 2003-07-02 | 2005-01-05 | Nissan Motor Co., Ltd. | Electrocatalyst and method of manufacturing the same |
CN101306365A (en) * | 2008-07-03 | 2008-11-19 | 上海交通大学 | Composite anode electrocatalyst for direct methanol fuel cell |
CN109244491A (en) * | 2018-08-06 | 2019-01-18 | 浙江高成绿能科技有限公司 | A kind of fuel cell Pt/WO3The preparation method of C catalyst |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113611886A (en) * | 2021-01-25 | 2021-11-05 | 南京工业大学 | Fuel cell electrocatalyst and preparation method thereof |
CN113611886B (en) * | 2021-01-25 | 2022-08-12 | 南京工业大学 | Fuel cell electrocatalyst and preparation method thereof |
CN112850787A (en) * | 2021-01-27 | 2021-05-28 | 浙江高成绿能科技有限公司 | Catalyst carrier for fuel cell, catalyst and preparation method thereof |
CN114843532A (en) * | 2022-05-09 | 2022-08-02 | 嘉庚创新实验室 | Preparation method of high-activity Pt/C catalyst |
CN114843532B (en) * | 2022-05-09 | 2023-12-19 | 嘉庚创新实验室 | Preparation method of high-activity Pt/C catalyst |
CN115784294A (en) * | 2022-11-22 | 2023-03-14 | 国家电投集团氢能科技发展有限公司 | Metal oxide carrier and preparation method and application thereof |
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