CN210092222U - Micro-channel circulating flow type pulse electrodeposition device for preparing platinum-based core-shell structure catalyst - Google Patents
Micro-channel circulating flow type pulse electrodeposition device for preparing platinum-based core-shell structure catalyst Download PDFInfo
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- CN210092222U CN210092222U CN201920464439.8U CN201920464439U CN210092222U CN 210092222 U CN210092222 U CN 210092222U CN 201920464439 U CN201920464439 U CN 201920464439U CN 210092222 U CN210092222 U CN 210092222U
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 39
- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 111
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- 238000007789 sealing Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
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- 239000010439 graphite Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 3
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- 229920003023 plastic Polymers 0.000 claims description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
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- 239000010453 quartz Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910020437 K2PtCl6 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004758 underpotential deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- Y02E60/50—Fuel cells
Abstract
The utility model discloses a microchannel circulating flow type pulse electrodeposition device for preparing platinum-based core-shell structure catalyst and a use method thereof. The device comprises a pulse direct-current power supply, a liquid circulating pump, a material container and a microchannel electrodeposition tank, wherein the microchannel electrodeposition tank comprises a material inlet, a material outlet and a group of S-shaped microchannels, when a material flows through the microchannels between two polar plates, an electrodeposition effect is generated under the action of a pulse external power supply, and active metal ions in a solution are deposited on the surfaces of metal or nitride nano particles serving as cores in the material to form a catalyst with a core-shell structure; after deposition is finished, the catalyst can be prepared by simple separation, washing and drying. The utility model provides a microchannel sets up the poor problem of preparation inefficiency, the catalyst homogeneity that makes that has effectively solved present macro-channel device existence, provides a highly reliable's preparation facilities for the batch preparation of nucleocapsid structure catalyst.
Description
Technical Field
The utility model relates to a preparation facilities of Pt base nuclear shell structure catalyst, concretely relates to microchannel circulation formula pulse electrodeposition device for preparing platinum base nuclear shell structure catalyst.
Background
The low-temperature proton exchange membrane fuel cell has the advantages of high energy conversion efficiency, high power density, low working temperature, zero emission and the like, and is a high-efficiency clean energy conversion device. However, large-scale commercialization of fuel cell technology still faces some problems, the most serious of which is the use of Pt catalysts in large quantities. Therefore, the development of low platinum and non-platinum catalysts has become the most important issue in the field of fuel cells.
The core-shell structure catalyst is a very important low platinum catalyst appearing in recent years, and the catalyst is a novel high-performance catalyst prepared by using nanoparticles of relatively cheap noble metals, transition metals, alloys and conductive compounds as cores and covering Pt with a single or a plurality of atomic layer thicknesses on the surfaces of the cores as shell layers. The core-shell structure low-platinum catalyst can greatly reduce the use amount of noble metal Pt of the fuel cell, further reduce the cost of the fuel cell, and is expected to realize large-scale commercialization of the proton exchange membrane fuel cell. Research on core-shell structure low platinum catalysts has become one of the most popular research subjects in the field of fuel cells. The difficulty in preparing the core-shell catalyst is that a single atomic layer or an ultrathin shell layer with the thickness of only a few atomic layers is prepared on the surface of the nano particle serving as a matrix.
The pulse electrodeposition method is generally prepared by a constant current pulse method, and the laboratory generally adopts a rotating disk electrode to complete the preparation, however, the rotating disk electrode has limited preparation amount (microgram level) at each time and is not suitable for the amplification preparation of the catalyst.
The chinese patent application CN108075144A invented a method for preparing a catalyst with noble metal as core and dense and copper-modified Pt as shell layer by underpotential deposition technique, but the core material of this method is only limited to the preparation of core-shell structured catalyst with metal as core.
The invention discloses a metal-coated oxide nano core-shell structure catalyst, which is invented by Chinese patent application CN102969514B, and uniformly distributed metal is used as a shell layer, and oxide nano particles are used as an inner core. Although the core-shell structure catalyst has good oxygen reduction activity, the preparation process is relatively complicated.
The chinese patent application CN105032460A discloses a low platinum catalyst based on nitride nanoparticles prepared by a pulse deposition technique. Although the method adopts a pulse deposition method to prepare the nitride-based low platinum catalyst with excellent performance, the patent does not relate to the invention of a pulse electrodeposition device.
In summary, no suitable preparation device is available for the scale-up preparation of the core-shell structure catalyst.
SUMMERY OF THE UTILITY MODEL
In order to overcome the defects of the prior art, the utility model aims to provide a micro-channel circulating flow type pulse electrodeposition device for preparing a platinum-based core-shell structure catalyst, which is suitable for preparing the core-shell structure catalyst in batches by an electrodeposition method.
The purpose of the utility model is realized through the following technical scheme.
A micro-channel circulating flow type pulse electrodeposition device for preparing a platinum-based core-shell structure catalyst comprises a first conductor material, a pulse direct-current power supply anode, an insulating seal ring, a material pipe, a pulse direct-current power supply cathode, a second conductor material, a material tank and a material discharging pipe; the first conductor material, the insulating seal ring and the second conductor material are sequentially arranged from top to bottom; the first conductor material is connected with the positive electrode of a pulse direct-current power supply, and the second conductor material is connected with the negative electrode of the pulse direct-current power supply; a microchannel electrodeposition tank is arranged in the insulating sealing ring and consists of a material inlet, a material outlet and more than one group of S-shaped microchannels; the material inlet and the material outlet are respectively connected with the inlet and the outlet of the S-shaped microchannel, namely the microchannel electrodeposition tank is a material inlet, and more than one group of S-shaped microchannels and material outlets are sequentially connected; the material inlet is connected with the material tank through a material pipe, and the material outlet is connected with the material tank through a material pipe.
In the device, a liquid circulating pump is arranged on the material pipe between the material inlet and the material tank.
In the device, the S-shaped micro-channel is a semicircular groove with the cross section of 2-20 mm in diameter or a rectangular groove with the cross section of 2-20 mm (depth) 2-20 mm (width).
In the above device, the material of the first conductive material is selected from graphite or metal; the material of the second conductor material is selected from graphite or metal.
In the above device, the insulating seal ring is made of various insulating plastic or silica gel insulating materials with sealing property; the material of the insulating sealing ring comprises polytetrafluoroethylene or polystyrene.
In the above device, the first conductive material, the insulating seal ring, and the second conductive material are fixed by bolts.
Preferably, the microchannel is formed by combining a first conductor material, a second conductor material and an insulating sealing gasket cut and processed according to a specific shape, and the specific structure is that a channel is formed in the insulating sealing gasket, and the upper part and the lower part of the channel are covered by the first conductor material 1 and the second conductor material.
When the material flows through the micro-channel on the polar plate, the utility model generates the electro-deposition effect under the effect of the pulse external power supply, the active metal ions (usually Pt) in the solution are deposited on the metal or nitride nano-particle surface as the core in the material to form the catalyst with the core-shell structure, the deposition amount, the deposition time and the like can be determined by adjusting the concentration, the flow rate and the pulse frequency of the material; after deposition is finished, the catalyst can be prepared by simple separation, washing and drying.
A use method of a micro-channel circulating flow type pulse electrodeposition device for preparing a platinum-based core-shell structure catalyst comprises the following steps:
s1: dissolving a Pt precursor compound, a surfactant and an electrolyte in a solvent to prepare a pulse liquid A;
s2: adding the core nano material into the pulse liquid A, and uniformly mixing the core nano material and the pulse liquid A by an ultrasonic method, stirring and the like to prepare a solution B;
s3: transferring the solution B into a material tank 8, respectively connecting the positive pole and the negative pole of a pulse direct-current power supply to an electrochemical workstation, and setting a pulse electrodeposition program as preparation work;
s4: starting a liquid circulating pump, conveying the mixed liquid B to a micro-channel electrodeposition pool through a material pipe at a flow rate of 1-5L/min, and returning the mixed liquid B to a material tank through a discharge pipe;
s5: starting a pulse program, and performing circulating flow type pulse electrodeposition on the microchannel electrodeposition pond between the first conductor material and the second conductor material;
s6: after the pulse program is stopped, discharging all liquid in the micro-channel electrodeposition pool through a discharge pipe, and stopping the work of the liquid circulating pump;
s7: and centrifuging, washing and drying the pulse liquid subjected to pulse treatment to obtain the required Pt-based core-shell structure catalyst.
In the method, in step S1, the concentration of the Pt precursor compound is 1-5 g/L, and the Pt precursor compound is H2PtCl6Or K2PtCl6(ii) a The concentration of the surfactant is 2-10 g/L, and the surfactant is polyvinylpyrrolidone; the electrolyte consists of sodium sulfate with the concentration of 0.1-0.5 mol/L and sulfuric acid with the concentration of 0.2-0.8 mol/L; the solvent is water.
In the above method, in step S2, the core nanomaterial is: TiN, WC, or a metal; the metal includes Pd or Au.
In the method, in step S3, the pulse program is that the pulse current is-50 mA to-800 mA; the pulse time is 0.003 s-0.03 s, the pulse interval time is 0.01-1.0 s, and the pulse making times is 20000-80000 times.
The utility model discloses a device can realize that shell metal atom is at the even and quick deposit on nuclear nanometer particle surface, and the catalyst structure that makes is even, the functional.
The utility model discloses device yardstick size can be according to the production scale needs design concrete specification.
The utility model discloses well device microchannel can make pulse in-process pulse current act on the nuclear material more evenly, guarantees that the Pt base core-shell structure catalyst that prepares is complete and effective.
Preferably, the pulse program is a galvanostatic pulse method, i.e. setting the required pulse current, the time of one pulse (Ton) and the time between each pulse (Toff).
Compared with the prior art, the utility model has the advantages that:
the utility model provides a microchannel sets up the poor problem of preparation inefficiency, the catalyst homogeneity that makes that has effectively solved present macro-channel device existence, provides a highly reliable's preparation facilities for the batch preparation of nucleocapsid structure catalyst. The batch preparation of the core-shell structure catalyst is possible.
Drawings
FIG. 1 is a schematic view of an electrodeposition apparatus according to the present invention;
FIG. 2 is a sectional view taken along line A-A of FIG. 1
FIG. 3 is a TEM image of the TiN @ Pt sample described in example 1;
FIG. 4 is a TEM micrograph of the TiN @ Pt sample described in example 1;
FIG. 5 is a graph of performance of samples prepared using this apparatus compared to Pt/C;
FIG. 6 is a TEM image of a sample of TiN @ Pt/NCNT as described in example 3.
Detailed Description
The following describes the embodiments of the present invention with reference to the examples and the accompanying drawings, but the embodiments of the present invention are not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
As shown in fig. 1 and fig. 2, the following embodiments adopt a device including a first conductor material 1, a positive electrode 2 of a pulse dc power supply, an insulating seal ring 3, a material pipe 4, a negative electrode 5 of the pulse dc power supply, a second conductor material 6, a material tank 8, and a discharge pipe 9; the first conductor material 1, the insulating seal ring 3 and the second conductor material 6 are sequentially arranged from top to bottom; the first conductor material 1 is connected with a positive electrode 2 of a pulse direct-current power supply, and the second conductor material 6 is connected with a negative electrode 5 of the pulse direct-current power supply; a micro-channel electrodeposition tank 10 is arranged in the insulating seal ring 3, and the micro-channel electrodeposition tank 10 consists of a material inlet, a material outlet and more than one group of S-shaped micro-channels; the material inlet and the material outlet are respectively connected with the inlet and the outlet of the S-shaped microchannel, namely the microchannel electrodeposition tank 10 is a material inlet, and more than one group of S-shaped microchannels and material outlets are sequentially connected; the material inlet is connected with the material tank 8 through the material pipe 4, and the material outlet is connected with the material tank 8 through the material discharging pipe 9. And a liquid circulating pump 7 is arranged on the material pipe 4 between the material inlet and the material tank 8. The S-shaped micro-channel is a semicircular groove with the cross section of 2-20 mm in diameter or a rectangular groove with the cross section of 2-20 mm in depth and 2-20 mm in width. The material of the first conductor material 1 is selected from graphite or metal; the material of the second conductor material 6 is selected from graphite or metal. The insulating seal ring 3 is made of various insulating plastic or silica gel insulating materials with sealing property; the material of the insulating sealing ring 3 comprises polytetrafluoroethylene or polystyrene. The first conductor material 1, the insulating seal ring 3 and the second conductor material 6 are fixed through bolts.
Example 1: TiN @ Pt catalyst
Preparation of TiN core nanoparticles
80mL of absolute ethanol was added to a Meng wash bottle, followed by 20mL of TiCl4. After ultrasonic (stirring) is uniform, ammonia gas is introduced until the number of formed precipitates is not increased any more; cutting off ammonia gas, covering a washing bottle, transferring into a vacuum drying oven, and drying and evaporating the solvent in the oven at 50 ℃ for 24 hours in vacuum to obtain an ammonia complex solid of titanium;
putting 500mg of complex solid into a quartz boat, putting into a quartz tube stone furnace, introducing high-purity nitrogen to replace air in a furnace tube, introducing ammonia water and starting to heat; controlling the flow rate of ammonia water at 10ml/min, and controlling the heating rate at 5 ℃/min; raising the temperature to 800 ℃, then nitriding at the constant temperature for two hours, then switching to high-purity nitrogen and beginning to cool, taking out after cooling to room temperature, and measuring by XRD to obtain the pure TiN with a face cube structure (card number: JCPDS NO. 38-1420).
2. Micro-channel circulating flow type pulse electrodeposition
20mL of a pulse solution (2.5 g/L H concentration)2PtCl6·6H2O, polyvinylpyrrolidone with the concentration of 6g/L, sodium sulfate with the concentration of 0.1mol/L and sulfuric acid with the concentration of 0.4 mol/L) and 20g of TiN, and then the mixture is stirred by ultrasonic for 1 hour, and is added into a material tank 8 after being mixed uniformly. Then, a direct current power supply is connected into the device through a pulse direct current power supply anode 2 and a pulse direct current power supply cathode 5, and a pulse electrodeposition program with the required pulse current of-150 mA, the time (Ton) of one pulse of 0.003s and the time (Toff) of the interval of each pulse of 0.03s is set as a preparation work. The microchannel is a semicircular groove with the cross section of 11mm, and the selected insulating gasket is a gasket processed by polytetrafluoroethylene. The liquid circulating pump 7 is started, and the proper peristaltic speed is adjusted to be 1 mL/min. The circulation of the mixed liquid from the material tank 8 is started and the mixed liquid is input from the material pipe 4 into the micro-channel electrodeposition tank 10 to prepare for the pulse deposition experiment. After the material flows out of the discharge pipe 9, a pulse program is started, and circulating pulse electrodeposition is carried out on the micro-channel 10 between the two conductor plates. After the pulse program is stopped, discharging all liquid in the S-shaped microchannel through a discharge pipe, and stopping the work of the peristaltic pump; and washing and drying the obtained material to obtain the required TiN @ Pt structure catalyst.
3. Structural morphology characterization and performance test of catalyst
(1) Structural morphology characterization of the catalyst:
the morphology of the nitride nanoparticles and the morphology of the platinum-deposited nitride nanoparticles were observed by a Transmission Electron Microscope (TEM) (fig. 3), and the average particle size of the titanium nitride prepared in this example was 8 to 11nm, and the particle size distribution was relatively uniform. As can be seen from FIG. 4, the platinum deposited by the pulse electrodeposition method does not form particles on the surface of the titanium nitride, and the lattice fringes of Pt and the titanium nitride can be clearly seen by using a high-resolution transmission electron microscope image, and the two fringes have obvious difference, which proves that the Pt is deposited in the atomic layer thickness level. The catalyst prepared in this example was found to have a platinum loading of 5.3 wt% as a result of ICP analysis.
(2) And (3) testing the catalytic performance of cathode oxygen reduction:
coating the collected core-shell structure catalyst on a glassy carbon electrode by adopting a three-electrode system, and carrying out oxygen saturation on 0.1M HClO4In the above, a linear voltammetric scan was performed at a sweep rate of 10mV/s and an electrode rotation rate of 1600r/min, and the results are shown in FIG. 5.
Example 2: TiNiN @ Pt catalyst
1. Preparing bimetallic nickel titanium nitride (TiNiN) core nanoparticles:
in a fume hood, 80mL of ethanol are added to the Meng wash bottle, followed by 20mL of TiCl4The solution and 1.697g of nickel acetate tetrahydrate were mixed and sufficiently dissolved with stirring, the atomic ratio of Ti to Ni was 19:1, and the other preparation procedures were the same as in example 1.
2. Preparing TiNiN @ Pt by adopting micro-channel circulating flow type pulse electrodeposition:
the procedure of example 1 was followed except that the microchannel was rectangular grooves of 10mm in depth by 20mm in width and the gasket was polystyrene-processed gasket.
The resulting core-shell TiNiN @ Pt catalyst had oxygen reduction activity that exceeded that of the commercial Pt/C catalyst, as shown in FIG. 5.
Example 3: TiN @ Pt/NCNT catalyst
1. Preparation of nitrogen-doped carbon nanotube (NCNT) loaded titanium nitride (TiN):
in a fume hood, 80mL of ethanol are added to the Meng wash bottle, followed by 5mL of TiCl4The solution and 17.5g of carbon nanotubes were stirred and mixed thoroughly, the mass ratio of the carbon carrier to the substrate being 80%. The procedure was otherwise the same as in example 1, and a TEM photograph of the obtained material is shown in FIG. 6.
2. The preparation of TiN @ Pt/NCNT by using micro-channel circulating flow type pulse electrodeposition is carried out in the same way as in example 1 except that the following points are different:
(1) pulse solution (platinum tetraammine dichloride, wherein the concentration of Pt is 5g/L, and 0.1M sodium sulfate and 0.125M sodium citrate);
(2) the pulse current is 100mA, the on-time is 0.3ms, and the off-time is 1.5ms
The catalyst prepared in this example had an oxygen reduction performance 3.9 times that of the commercial Pt/C catalyst.
The above embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. A micro-channel circulating flow type pulse electrodeposition device for preparing a platinum-based core-shell structure catalyst is characterized by comprising a first conductor material (1), a pulse direct-current power supply anode (2), an insulating seal ring (3), a material pipe (4), a pulse direct-current power supply cathode (5), a second conductor material (6), a material tank (8) and a discharge pipe (9); the first conductor material (1), the insulating sealing ring (3) and the second conductor material (6) are sequentially arranged from top to bottom; the first conductor material (1) is connected with a positive pole (2) of a pulse direct-current power supply, and the second conductor material (6) is connected with a negative pole (5) of the pulse direct-current power supply; a micro-channel electrodeposition pool (10) is arranged in the insulating seal ring (3), and the micro-channel electrodeposition pool (10) consists of a material inlet, a material outlet and more than one group of S-shaped micro-channels; the material inlet and the material outlet are respectively connected with the inlet and the outlet of the S-shaped microchannel, namely the microchannel electrodeposition tank (10) is a material inlet, and more than one group of S-shaped microchannels and material outlets are sequentially connected; the material inlet is connected with the material tank (8) through a material pipe (4), and the material outlet is connected with the material tank (8) through a material discharging pipe (9).
2. The microchannel circulating flow type pulse electrodeposition device for preparing the platinum-based core-shell structured catalyst according to claim 1, wherein a liquid circulating pump (7) is disposed on the material pipe (4) between the material inlet and the material tank (8).
3. The device for preparing the platinum-based core-shell catalyst through the microchannel circulating flow type pulse electrodeposition according to claim 1, wherein the S-shaped microchannel is a semicircular groove with a cross section of 2-20 mm in diameter or a rectangular groove with a cross section of 2-20 mm by 2-20 mm.
4. The microchannel circulating flow type pulse electrodeposition apparatus for preparing a platinum-based core-shell structure catalyst according to claim 1, wherein the material of the first conductor material (1) is selected from graphite or metal; the material of the second conductor material (6) is selected from graphite or metal.
5. The microchannel circulating flow type pulse electrodeposition device for preparing a platinum-based core-shell structured catalyst according to claim 1, wherein the material of the insulating seal ring (3) comprises various insulating plastic or silica gel insulating materials with sealing property; the insulating sealing ring (3) is made of polytetrafluoroethylene or polystyrene.
6. The microchannel circulating flow type pulse electrodeposition device for preparing the platinum-based core-shell structure catalyst according to claim 1, wherein the first conductor material (1), the insulating seal ring (3) and the second conductor material (6) are fixed by bolts.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201920464439.8U CN210092222U (en) | 2019-04-08 | 2019-04-08 | Micro-channel circulating flow type pulse electrodeposition device for preparing platinum-based core-shell structure catalyst |
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| CN201920464439.8U CN210092222U (en) | 2019-04-08 | 2019-04-08 | Micro-channel circulating flow type pulse electrodeposition device for preparing platinum-based core-shell structure catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112423A (en) * | 2019-04-08 | 2019-08-09 | 华南理工大学 | A kind of microchannel recycle stream dynamic formula pulse electrodeposition device being used to prepare platinum base catalyst with core-casing structure and its application method |
-
2019
- 2019-04-08 CN CN201920464439.8U patent/CN210092222U/en not_active Withdrawn - After Issue
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112423A (en) * | 2019-04-08 | 2019-08-09 | 华南理工大学 | A kind of microchannel recycle stream dynamic formula pulse electrodeposition device being used to prepare platinum base catalyst with core-casing structure and its application method |
| CN110112423B (en) * | 2019-04-08 | 2024-02-09 | 华南理工大学 | Microchannel circulating flow type pulse electrodeposition device for preparing platinum-based core-shell structure catalyst and application method thereof |
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