CN112952120A - Preparation method of Co3O4/NiPdCo alloy/graphene composite material - Google Patents
Preparation method of Co3O4/NiPdCo alloy/graphene composite material Download PDFInfo
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- CN112952120A CN112952120A CN202110140054.8A CN202110140054A CN112952120A CN 112952120 A CN112952120 A CN 112952120A CN 202110140054 A CN202110140054 A CN 202110140054A CN 112952120 A CN112952120 A CN 112952120A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 47
- 239000000956 alloy Substances 0.000 title claims abstract description 36
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 26
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 19
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims abstract description 15
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 claims abstract description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000002244 precipitate Substances 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 229910021397 glassy carbon Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- 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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Abstract
The invention discloses a Co3O4The preparation method of the/NiPdCo alloy/graphene composite material comprises the following steps: firstly, carrying out hydrothermal reaction on palladium acetylacetonate, cobalt nitrate, nickel nitrate and 1, 2-hexadecanediol; adding polyvinyl alcohol and ethylenediamine into a water bath, and carrying out hydrothermal stirring to obtain a NiPdCo alloy; thirdly, after dissolving the cobalt nitrate, adjusting the pH value, aging and calcining to obtain Co3O4(ii) a Finally, NiPdCo alloy and Co3O4Mixing with graphene, stirring, and drying to obtain Co3O4The NiPdCo alloy/graphene composite material. Co prepared by the invention3O4the/NiPdCo alloy/graphene composite material hasGood electrocatalytic activity, can effectively catalyze the oxygen reduction reaction and has good stability.
Description
Technical Field
The invention relates to the field of nano catalysts, in particular to Co3O4A preparation method of a/NiPdCo alloy/graphene composite material.
Background
Fuel cells are receiving much attention due to the characteristics of environmental protection and high energy density, but the retarded cathode oxygen reduction kinetic reaction (ORR) is a big obstacle to their development. The problem of slow reaction of cathode oxygen reduction can be effectively solved by using the cathode oxygen reduction catalyst. At present, the mainly used cathode catalyst is a noble metal catalyst which has excellent catalytic activity and can effectively catalyze the oxygen reduction reaction, but the noble metal catalyst is based on non-noble metals due to high cost and low storage capacityThe research of the catalyst has important promotion effect on the development of the fuel cell. In the transition metal oxides, Co3O4The price is low, and the stability in alkaline solution is good, thereby receiving more attention. Due to Co3O4The conductivity is poor, the catalytic activity is poor, and the catalyst cannot be directly used as an oxygen reduction catalyst, and the problem can be effectively solved by compounding the catalyst with other compounds.
Disclosure of Invention
Aiming at the problems, the invention discloses Co3O4The preparation method of the/NiPdCo alloy/graphene composite material comprises the following steps:
s1: adding palladium acetylacetonate, cobalt nitrate and nickel nitrate into a mixed solution of toluene and ethanol, adding 1, 2-hexadecanediol, stirring for 1-2h, transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction;
s2: placing the solution after the S1 reaction in a water bath, adding polyvinyl alcohol and ethylene diamine, heating to 300 ℃ at 220 ℃, stirring for 4-6h, cooling, transferring the solution into a centrifuge tube, centrifugally separating a product, cleaning the product with deionized water and ethanol, and then placing the product in a drying oven for drying;
s3: adding cobalt nitrate into deionized water, and adding 0.8-1mol/L of Na in a stirring environment2CO3Dropwise adding the solution into a cobalt nitrate solution, adjusting the pH value of the solution to 9-9.5, aging and standing the solution for 3 hours, filtering the precipitate, fully washing the precipitate with distilled water, drying the precipitate, transferring the dried precipitate into a muffle furnace, and calcining the dried precipitate for 3-5 hours at the temperature of 400 ℃ and 600 ℃;
s4: adding graphene into deionized water, performing ultrasonic treatment to completely disperse graphene, adding products S2 and S3, stirring for 1-2h, standing for 2h, filtering the precipitate, cleaning with deionized water and ethanol for 3-5 times, and vacuum drying at 60 ℃ for 6-8h to obtain Co3O4The NiPdCo alloy/graphene composite material.
Preferably, in step S1, the mass ratio of palladium acetylacetonate, cobalt nitrate, nickel nitrate and 1, 2-hexadecanediol is 1: (1.5-2): (1.5-2): (2-3).
Preferably, in step S1, the volume ratio of toluene to ethanol is 1: (2-3).
Preferably, in the step S1, the temperature of the hydrothermal reaction is 120-150 ℃, and the reaction time is 6-8 h.
Preferably, in step S2, the mass-to-volume ratio of palladium acetylacetonate to polyvinyl alcohol and ethylenediamine is 1 g: (1-1.5) ml: (0.5-1) ml.
Preferably, in the step S3, the mass ratio of the cobalt nitrate to the palladium acetylacetonate in S1 is 1: 1.
Preferably, in step S4, the mass ratio of graphene to platinum acetylacetonate is (2-3): 1.
compared with the prior art, the invention has the following beneficial effects:
(1) the ternary NiPdCo alloy is synthesized in a liquid phase by using palladium acetylacetonate as a palladium source, cobalt nitrate as a cobalt source, nickel nitrate as a nickel source, 1, 2-hexadecanediol as a reducing agent and polyvinyl alcohol and ethylenediamine as surfactants.
(2) The NiPdCo alloy has good catalytic performance and good conductivity, reduces the use of palladium acetylacetonate and reduces the cost.
(3) Mixing NiPdCo alloy and Co3O4The graphene is loaded on graphene together, so that the conductivity of the catalyst is improved, the catalyst has a larger specific surface area, the ORR catalytic capability is improved, and the electrocatalytic stability of the material can be improved.
(4) The raw materials used in the invention have wide sources, and the preparation method is simple and is suitable for large-scale production.
Drawings
FIG. 1 shows Co prepared in example 1 of the present invention3O4LSV curve diagram of/NiPdCo alloy/graphene composite material and Pt/C.
FIG. 2 shows Co prepared in example 1 of the present invention3O4The polarization curve of the NiPdCo alloy/graphene composite material after durability test in 0.1M KOH electrolyte after 8000 cycles.
FIG. 3 is a polarization curve after durability testing in 0.1M KOH electrolyte after 8000 Pt/C cycles.
Detailed Description
Example 1:
co3O4The NiPdCo alloy/graphene composite material is prepared by the following method:
s1: adding 1g of palladium acetylacetonate, 1.8g of cobalt nitrate and 1.8g of nickel nitrate into a mixed solution of 10ml of toluene and 25ml of ethanol, adding 2.5g of 1, 2-hexadecanediol, stirring for 1.5h, transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 140 ℃ for 7 h;
s2: placing the solution obtained after the reaction of S1 in a water bath, adding 1.2ml of polyvinyl alcohol and 0.8ml of ethylenediamine, heating to 250 ℃, stirring for 5 hours, cooling, transferring the solution into a centrifuge tube, centrifugally separating out a product, washing the product for 4 times by using deionized water and ethanol, and then placing the product in a drying oven for drying;
s3: adding 1g of cobalt nitrate into deionized water, and adding 0.9mol/L of Na in a stirring environment2CO3Dropwise adding the solution into a cobalt nitrate solution, adjusting the pH value of the solution to 9.2, aging and standing the solution for 3 hours, filtering the precipitate, fully washing the precipitate with distilled water, drying the precipitate, transferring the dried precipitate into a muffle furnace, and calcining the dried precipitate at 500 ℃ for 4 hours;
s4: adding 2.5g of graphene into deionized water, performing ultrasonic treatment for 30min to completely disperse the graphene, then adding products S2 and S3, stirring for 1.5h, standing for 2h, filtering the precipitate, washing the precipitate with deionized water and ethanol for 4 times, and performing vacuum drying at 60 ℃ for 7h to obtain Co3O4The NiPdCo alloy/graphene composite material.
Example 2:
co3O4The NiPdCo alloy/graphene composite material is prepared by the following method:
s1: adding 1g of palladium acetylacetonate, 1.5g of cobalt nitrate and 1.5g of nickel nitrate into a mixed solution of 10ml of toluene and 20ml of ethanol, adding 2g of 1, 2-hexadecanediol, stirring for 1h, transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 8 h;
s2: placing the solution obtained after the reaction of S1 in a water bath, adding 1ml of polyvinyl alcohol and 0.5ml of ethylenediamine, heating to 220 ℃, stirring for 6 hours, cooling, transferring the solution into a centrifuge tube, centrifugally separating a product, washing the product for 3 times by deionized water and ethanol, and then placing the product in a drying oven for drying;
s3: adding 1g of cobalt nitrate into deionized water, and adding 0.8mol/L of Na in a stirring environment2CO3Dropwise adding the solution into a cobalt nitrate solution, adjusting the pH value of the solution to 9, aging and standing the solution for 3 hours, filtering the precipitate, fully washing the precipitate with distilled water, drying the precipitate, transferring the dried precipitate into a muffle furnace, and calcining the dried precipitate at 400 ℃ for 5 hours;
s4: adding 2g of graphene into deionized water, performing ultrasonic treatment for 20min to completely disperse the graphene, then adding products S2 and S3, stirring for 1h, standing for 2h, filtering the precipitate, washing the precipitate with deionized water and ethanol for 3 times, and performing vacuum drying at 60 ℃ for 6h to obtain Co3O4The NiPdCo alloy/graphene composite material.
Example 3:
co3O4The NiPdCo alloy/graphene composite material is prepared by the following method:
s1: adding 1g of palladium acetylacetonate, 2g of cobalt nitrate and 2g of nickel nitrate into a mixed solution of 10ml of toluene and 30ml of ethanol, adding 3g of 1, 2-hexadecanediol, stirring for 2 hours, transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 6 hours at 150 ℃;
s2: placing the solution obtained after the reaction of S1 in a water bath, adding 1.5ml of polyvinyl alcohol and 1ml of ethylenediamine, heating to 300 ℃, stirring for 4 hours, cooling, transferring the solution into a centrifuge tube, centrifugally separating a product, washing the product with deionized water and ethanol for 5 times, and then placing the product in a drying oven for drying;
s3: adding 1g of cobalt nitrate into deionized water, and adding 1mol/L of Na in a stirring environment2CO3Dropwise adding the solution into a cobalt nitrate solution, adjusting the pH value of the solution to 9.5, aging and standing the solution for 3 hours, filtering precipitates, fully washing the precipitates with distilled water, drying the precipitates, transferring the precipitates into a muffle furnace, and calcining the precipitates for 3 hours at 600 ℃;
s4: adding 3g of graphene into deionized water, performing ultrasonic treatment for 40min to completely disperse the graphene, then adding products S2 and S3, stirring for h, standing for 2h, filtering the precipitate, washing the precipitate with deionized water and ethanol for 5 times, and performing vacuum drying at 60 ℃ for 8h to obtain Co3O4Composite of/NiPdCo alloy/grapheneA material.
Example 4:
co3O4The NiPdCo alloy/graphene composite material is prepared by the following method:
s1: adding 1g of palladium acetylacetonate, 1.5g of cobalt nitrate and 2g of nickel nitrate into a mixed solution of 10ml of toluene and 25ml of ethanol, adding 3g of 1, 2-hexadecanediol, stirring for 1.5h, transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 7h at 130 ℃;
s2: placing the solution obtained after the reaction of S1 in a water bath, adding 1.1ml of polyvinyl alcohol and 0.9ml of ethylenediamine, heating to 250 ℃, stirring for 5 hours, cooling, transferring the solution into a centrifuge tube, centrifugally separating out a product, washing the product for 4 times by using deionized water and ethanol, and then placing the product in a drying oven for drying;
s3: adding 1g of cobalt nitrate into deionized water, and adding 0.9mol/L of Na in a stirring environment2CO3Dropwise adding the solution into a cobalt nitrate solution, adjusting the pH value of the solution to 9.1, aging and standing the solution for 3 hours, filtering the precipitate, fully washing the precipitate with distilled water, drying the precipitate, transferring the dried precipitate into a muffle furnace, and calcining the dried precipitate at 500 ℃ for 4 hours;
s4: adding 2.5g of graphene into deionized water, performing ultrasonic treatment for 30min to completely disperse the graphene, then adding products S2 and S3, stirring for 1.5h, standing for 2h, filtering the precipitate, washing the precipitate with deionized water and ethanol for 4 times, and performing vacuum drying at 60 ℃ for 7h to obtain Co3O4The NiPdCo alloy/graphene composite material.
And (3) performance testing:
oxygen Reduction Reaction (ORR) test: the ORR performance of the sample was tested by Chenghua CHI760E electrochemical workstation using RDE by Linear Sweep Voltammetry (LSV), electrolyte was 0.1M KOH, oxygen was passed until saturation before the test, sweep range was (0.2V-1.0V), sweep rate was 10 mV. s-1The rotating disc electrode speed was 1600 rpm.
The test process adopts a three-electrode system: wherein, the working electrode is glassy carbon electrode RDE (5mm, Pine); the reference electrode used was an Ag/AgCl electrode, the electrode fill was a 3M KCl solution, the standard electrode potential in 0.1M KOH solution was 0.949V versus a reversible oxygen electrode, and the counter electrode used was a Pt electrode.
The glassy carbon electrode needs to be pretreated to a certain extent before being used, and the electrode is cleaned. The cleaning steps are as follows: before use, 1.0um and 0.5um aluminum oxide powder are used for polishing the electrode in sequence until the surface of the electrode is observed to be bright and smooth like a mirror, and the glassy carbon electrode polished by the aluminum oxide powder is washed by deionized water and then dried at room temperature. The main purpose is to remove the pollutants on the surface, keep the electrode surface clean and flat and reduce the influence of other substances on the electrode surface on the test. Before testing the sample, the sample is dispersed in the solution to prepare a suspension dispersion liquid of the catalyst, the suspension dispersion liquid is dripped on the glassy carbon electrode, and the sample is uniformly and flatly dispersed on the surface of the glassy carbon electrode.
Preparation of a working electrode: 10mg of the catalyst prepared in examples 1 to 4 was ultrasonically dispersed in a mixed solution containing 1.2ml of ethanol and 0.08ml of Nafion (5%). And (4) dripping the dispersion liquid on the surface of the polished glassy carbon electrode, and naturally airing at room temperature. For comparison, a Pt/C catalyst was prepared as an electrode in the same manner.
For Co prepared in the invention example 13O4the/NiPdCo alloy/graphene composite material and Pt/C were subjected to LSV test at 1600rpm, as shown in FIG. 1, wherein the abscissa is voltage compared to a standard hydrogen electrode and the ordinate is current density, and Co prepared in example 1 of the present invention3O4The initial potential of the/NiPdCo alloy/graphene composite material is 0.98V, higher than 0.92V of Pt/C and closer to the standard potential E of the composite materialθ1.23V, while Co prepared in inventive example 13O4The half-wave potential of the/NiPdCo alloy/graphene composite material and the half-wave potential of the Pt/C are respectively 0.84V and 0.78V, which proves that the Co prepared in the embodiment 1 of the invention3O4The performance of the/NiPdCo alloy/graphene composite material in catalyzing ORR is superior to that of Pt/C.
The cycle stability was tested by subjecting the catalyst to a temperature of 50 mV.s-1Accelerated degradation experiments (ADT, voltage range: 0.2-1.0V/vs. RHE) were carried out for 8000 cycles of the catalyst prepared in example 1 and Pt/C, respectively. As can be seen from FIGS. 2 and 3, the operation was carried out after 8000 cyclesThe half-wave potential of the catalyst prepared in example 1 shifted by 15mV, but after 8000 cycles, the commercial Pt/C catalyst shifted by 69mV, indicating that the catalyst prepared in example 1 exhibited better cycle stability than Pt/C during the long cycle.
Co prepared in examples 2-4 of the invention3O4The performance data of the/NiPdCo alloy/graphene composite material are shown in Table 1, Table 1: initial potential and half-wave potential of examples 2 to 4
| Example 2 | Example 3 | Example 4 | |
| Initial potential (V) | 0.97 | 0.96 | 0.98 |
| Half-wave potential (V) | 0.82 | 0.82 | 0.83 |
It can be seen from table 1 that the starting potential and half-wave potential of the materials prepared in examples 2-4 of the present invention are similar to those of example 1, demonstrating that they also have good electrocatalytic activity.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same, although the present invention is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. Co3O4The preparation method of the/NiPdCo alloy/graphene composite material is characterized by comprising the following steps of:
s1: adding palladium acetylacetonate, cobalt nitrate and nickel nitrate into a mixed solution of toluene and ethanol, adding 1, 2-hexadecanediol, stirring for 1-2h, transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction;
s2: placing the solution after the S1 reaction in a water bath, adding polyvinyl alcohol and ethylene diamine, heating to 300 ℃ at 220 ℃, stirring for 4-6h, cooling, transferring the solution into a centrifuge tube, centrifugally separating a product, cleaning the product with deionized water and ethanol, and then placing the product in a drying oven for drying;
s3: adding cobalt nitrate into deionized water, and adding 0.8-1mol/L of Na in a stirring environment2CO3Dropwise adding the solution into a cobalt nitrate solution, adjusting the pH value of the solution to 9-9.5, aging and standing the solution for 3 hours, filtering the precipitate, fully washing the precipitate with distilled water, drying the precipitate, transferring the dried precipitate into a muffle furnace, and calcining the dried precipitate for 3-5 hours at the temperature of 400 ℃ and 600 ℃;
s4: adding graphene into deionized water, performing ultrasonic treatment to completely disperse graphene, adding products S2 and S3, stirring for 1-2h, standing for 2h, filtering the precipitate, cleaning with deionized water and ethanol for 3-5 times, and vacuum drying at 60 ℃ for 6-8h to obtain Co3O4The NiPdCo alloy/graphene composite material.
2. A Co as claimed in claim 13O4The preparation method of the/NiPdCo alloy/graphene composite material is characterized in that in the step S1, palladium acetylacetonate and nitric acid are usedThe mass ratio of cobalt to nickel nitrate to 1, 2-hexadecanediol is 1: (1.5-2): (1.5-2): (2-3).
3. A Co as claimed in claim 13O4The preparation method of the/NiPdCo alloy/graphene composite material is characterized in that in the step S1, the volume ratio of toluene to ethanol is 1: (2-3).
4. A Co as claimed in claim 13O4The preparation method of the/NiPdCo alloy/graphene composite material is characterized in that in the step S1, the temperature of the hydrothermal reaction is 120-150 ℃, and the reaction time is 6-8 h.
5. A Co as claimed in claim 13O4The preparation method of the/NiPdCo alloy/graphene composite material is characterized in that in the step S2, the mass-volume ratio of palladium acetylacetonate to polyvinyl alcohol to ethylenediamine is 1 g: (1-1.5) ml: (0.5-1) ml.
6. A Co as claimed in claim 13O4The preparation method of the/NiPdCo alloy/graphene composite material is characterized in that in the step S3, the mass ratio of cobalt nitrate to palladium acetylacetonate in S1 is 1: 1.
7. A Co as claimed in claim 13O4The preparation method of the/NiPdCo alloy/graphene composite material is characterized in that in the step S4, the mass ratio of graphene to platinum acetylacetonate is (2-3): 1.
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| US20080280753A1 (en) * | 2004-10-06 | 2008-11-13 | Yamanashi University | Method for Producing Electrocatalyst |
| CN102329976A (en) * | 2011-09-06 | 2012-01-25 | 上海交通大学 | Preparation method of graphene reinforced metal-matrix composite |
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| CN105727993A (en) * | 2016-01-20 | 2016-07-06 | 湖北大学 | Fct-phase FePtCu ternary alloy nano particle catalyst and synthesis method thereof |
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| US20080280753A1 (en) * | 2004-10-06 | 2008-11-13 | Yamanashi University | Method for Producing Electrocatalyst |
| CN102329976A (en) * | 2011-09-06 | 2012-01-25 | 上海交通大学 | Preparation method of graphene reinforced metal-matrix composite |
| CN102814178A (en) * | 2012-08-23 | 2012-12-12 | 南京理工大学 | Palladium-transition metal oxide-graphene ternary composite catalyst and preparation method thereof |
| CN105727993A (en) * | 2016-01-20 | 2016-07-06 | 湖北大学 | Fct-phase FePtCu ternary alloy nano particle catalyst and synthesis method thereof |
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