CN110112423A - 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 - Google Patents
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 Download PDFInfo
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- CN110112423A CN110112423A CN201910277682.3A CN201910277682A CN110112423A CN 110112423 A CN110112423 A CN 110112423A CN 201910277682 A CN201910277682 A CN 201910277682A CN 110112423 A CN110112423 A CN 110112423A
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- electrodeposition
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 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 109
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000004020 conductor Substances 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000012089 stop solution Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 11
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 239000011258 core-shell material Substances 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 9
- 150000004767 nitrides Chemical class 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 150000001455 metallic ions Chemical class 0.000 abstract description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 14
- 239000000446 fuel Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011824 nuclear material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000001509 sodium citrate Substances 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
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010408 sweeping Methods 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
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of microchannel recycle stream dynamic formula pulse electrodeposition device for being used to prepare platinum base catalyst with core-casing structure and its application methods.The device includes pulse dc power, liquid circulation pump, material container and microchannel electrodeposition bath, microchannel electrodeposition bath includes the microchannel of material inlet, material outlet and one group of S type, when material flows through the microchannel between two pieces of pole plates, electro-deposition effect is generated under the action of pulse external power, the active metallic ion in solution is deposited on the catalyst that the metal or nitride nano particle surface as core in material form core-shell structure；After the completion of deposition, catalyst can be prepared by by simply separating, washing, dry.Microchannel setting proposed by the present invention efficiently solves the problems, such as that preparation efficiency existing for current macro lane device is low, catalyst uniformity obtained is poor, provides a kind of highly reliable preparation facilities for the batch preparation of catalyst with core-casing structure.
Description
Technical field
The present invention relates to the preparation facilities of Pt base catalyst with core-casing structure, and in particular to one kind is used to prepare platinum base nucleocapsid knot
The microchannel recycle stream dynamic formula pulse electrodeposition device of structure catalyst, and realize that Pt base core-shell structure is catalyzed using this device
It is prepared by the amplification of the method for agent.
Background technique
Low-temperature protonic exchange film fuel battery has high energy conversion efficiency, power density height, operating temperature low and zero-emission
The advantages that putting is a kind of energy conversion apparatus of high-efficiency cleaning.However, the large-scale commercial of fuel cell technology still suffers from
Some problems, wherein problem the severeest is largely to use Pt catalyst.Therefore, develop low platinum and non-platinum catalyst has become
For the mostly important project of fuel cell field.
Catalyst with core-casing structure is the extremely important low-platinum catalyst of one kind occurred in recent years, this kind of catalyst be using
Relatively inexpensive noble metal, transition metal, alloy and conductive compound nanoparticle as core, on its surface covering it is single or
The Pt of several atomic layer level thickness is novel high-performance catalyst prepared by shell.Core-shell structure low-platinum catalyst can significantly drop
The usage amount of the precious metals pt of low fuel battery, and then the cost of fuel cell is reduced, it is to realize Proton Exchange Membrane Fuel Cells
Where the hope of large-scale commercial.It is most popular that research in relation to core-shell structure low-platinum catalyst has become fuel cell field
One of research topic.The difficult point of catalyst with core-casing structure preparation is to prepare in the nanoparticle surface as matrix monatomic
The ultra-thin shell of layer or only several atomic layer level thickness.
Pulse electrodeposition method generally uses constant current impulse method to prepare, and laboratory generally uses rotating disk electrode (r.d.e) to complete
Preparation, however, the amount that rotating disk electrode (r.d.e) is prepared every time is limited (Gamma Magnitude), is not suitable for the amplification system of this kind of catalyst
It is standby.
Chinese invention patent application CN108075144A has invented a kind of utilization underpotential deposition technology, is prepared for your gold
Belonging to is core, and having fine and close, copper modification Pt is the method for the catalyst of shell, but the method nuclear material is limited solely by preparation
Metal is the catalyst with core-casing structure of core.
Chinese invention patent application CN102969514B has invented a kind of metallic cover oxidate nano core-shell structure catalysis
Agent, by equally distributed metal as shell, oxide nano particles are as kernel.Although the catalyst with core-casing structure possesses not
Wrong oxygen reduction activity, but the relatively cumbersome complexity of preparation process.
Chinese invention patent application CN105032460A discloses a kind of using pulse deposition technique, prepares one kind and is based on
The low-platinum catalyst of nitride nano particle.Although this method prepares out the nitride with excellent properties using pulsed deposition method
Base low-platinum catalyst, but the invention of pulse electrodeposition device is not directed in patent.
In conclusion prepared by the amplification for catalyst with core-casing structure, suitable preparation facilities there is no at present.
Summary of the invention
For overcome the deficiencies in the prior art, the object of the present invention is to provide one kind to be used to prepare the catalysis of platinum base core-shell structure
The microchannel recycle stream dynamic formula pulse electrodeposition device and its application method of agent, the device and method are suitable for electro-deposition method batch
Amount prepares catalyst with core-casing structure.
The purpose of the present invention is achieved through the following technical solutions.
A kind of microchannel recycle stream dynamic formula pulse electrodeposition device being used to prepare platinum base catalyst with core-casing structure, including the
One conductor material, pulse dc power anode, insulated enclosure circle, materail tube, pulse dc power cathode, the second conductor material,
Material pot and discharge nozzle；The first conductor material, insulated enclosure circle and the second conductor material are successively arranged from top to bottom；It is described
First conductor material is connect with pulse dc power anode, and the second conductor material is connect with pulse dc power cathode；Institute
It states and is provided with microchannel electrodeposition bath in insulated enclosure circle, the microchannel electrodeposition bath is by material inlet, material outlet and one
The microchannel of S type more than group forms；The material inlet and material outlet connect with the entrance and exit of the microchannel of S type respectively
It connects, i.e., the described microchannel electrodeposition bath is that material inlet, the microchannel of one group or more of S type and material outlet are sequentially connected with；Institute
It states material inlet to connect by materail tube with material pot, the material outlet is connect by discharge nozzle with material pot.
In above-mentioned apparatus, liquid circulation pump is provided on the materail tube between the material inlet and material pot.
In above-mentioned apparatus, the microchannel of the S type is the semi-circular grooves or cross section that cross section is 2~20mm of diameter
For the rectangular grooves of 2~20mm (depth) * 2~20mm (width).
In above-mentioned apparatus, the material of the first conductor material is selected from graphite or metal；The second conductor material
Material is selected from graphite or metal.
In above-mentioned apparatus, the material of the insulated enclosure circle includes the various ambroin or silicone insulation for sealing attribute
Material；The material of the insulated enclosure circle includes polytetrafluoroethylene (PTFE) or polystyrene.
In above-mentioned apparatus, it is bolted between the first conductor material, insulated enclosure circle and the second conductor material.
Preferably, the microchannel is by the first conductor material, the second conductor material and according to specific shape cutting processing mistake
Insulated enclosure gasket be composed, specific structure is to offer channel in insulated enclosure gasket, channel it is upper and lower by first
Conductor material 1 and the covering of the second conductor material.
When material flows through the microchannel on pole plate in the present invention, electro-deposition effect is generated under the action of pulse external power,
Active metallic ion (usually Pt) in solution is deposited on the metal or nitride nano particle table as core in material
Face forms the catalyst of core-shell structure, and deposition and sedimentation time etc. can pass through concentration, flow velocity and the pulse of adjusting material
Frequency determine；After the completion of deposition, catalyst can be prepared by by simply separating, washing, dry.
A kind of use for the microchannel recycle stream dynamic formula pulse electrodeposition device being used to prepare platinum base catalyst with core-casing structure
Method, comprising the following steps:
S1: taking Pt precursor compound, surfactant and electrolyte dissolution in solvent, is made into pulse liquid A；
S2: taking core nano material that pulse liquid A is added makes it after mixing by processing such as ultrasonic method, stirrings, is made into molten
Liquid B；
S3: solution B is transferred in material pot 8, then pulse dc power anode and pulse dc power cathode are distinguished
It is connected on electrochemical workstation, and sets pulse electrodeposition program as preparation；
S4: start liquid circulating pump makes mixed liquid B be delivered to microchannel electricity via materail tube with the flow velocity of 1~5L/min
Sedimentation basin, and material pot is returned to by discharge nozzle；
S5: starting impulse program, the microchannel electrodeposition bath between the first conductor material and the second conductor material carry out
Recycle stream dynamic formula pulse electrodeposition；
S6: after pulse protocol stopping, by liquid whole in the electrodeposition bath of microchannel after discharge nozzle is discharged, stop liquid
The work of circulating pump；
S7: will treated after pulse liquid is centrifuged, washed and dried is that required Pt base core-shell structure is urged through pulse
Agent.
In the above method, in step S1, the concentration of Pt precursor compound is 1~5g/L, the Pt precursor compound
For H2PtCl6Or K2PtCl6；The concentration of the surfactant is 2~10g/L, and the surfactant is polyvinylpyrrolidine
Ketone；The sulfuric acid that the sodium sulphate that the electrolyte is 0.1~0.5mol/L by concentration is 0.2~0.8mol/L with concentration forms；Institute
Stating solvent is water.
In the above method, in step S2, the core nano material are as follows: TiN, WC or metal；The metal includes Pd or Au.
In the above method, in step S3, the pulse protocol is that pulse current is -50mA~-800mA；Burst length is
0.003s~0.03s, each interpulse period are set as 0.01~1.0s, and pulse number processed is 20000~80000 times.
The device of the invention can realize shell metallic atom in the uniform and fast deposition of core nanoparticle surface, it is obtained
Catalyst structure is uniform, functional.
Apparatus of the present invention scale size can need to design concrete specification according to production scale.
Device microchannel can be such that pulse current in pulse process more uniformly acts on nuclear material in the present invention, guarantee
Prepared Pt base catalyst with core-casing structure is complete and effective.
Preferably, it is the primary time of pulse current, pulse needed for being arranged that the pulse protocol, which is constant current impulse method,
(Ton) with interpulse period (Toff) each time.
Compared with prior art, present invention has an advantage that
It is low, obtained that microchannel setting proposed by the present invention efficiently solves preparation efficiency existing for current macro lane device
Catalyst uniformity difference problem, provide a kind of highly reliable preparation dress for the batch preparation of catalyst with core-casing structure
It sets.So that the batch of catalyst with core-casing structure is prepared into possibility.
Detailed description of the invention
Fig. 1 is electric deposition device schematic diagram of the present invention；
Fig. 2 is the figure of TiN@Pt sample TEM described in example 1；
Fig. 3 is TiN@Pt sample TEM enlarged drawing described in example 1；
Fig. 4 is the performance map using sample prepared by this device and Pt/C comparison；
Fig. 5 is the figure of TiN@Pt/NCNT sample TEM described in example 3.
Specific embodiment
The specific implementation of the invention patent is described further below in conjunction with example and attached drawing, but embodiment party of the invention
Formula is without being limited thereto.For not specifically specified technological parameter, routine techniques progress can refer to.
As depicted in figs. 1 and 2, following embodiment uses following device, including the first conductor material 1, pulse dc power
Anode 2, insulated enclosure circle 3, materail tube 4, pulse dc power cathode 5, the second conductor material 6, material pot 8 and discharge nozzle 9；Institute
The first conductor material 1, insulated enclosure circle 3 and the second conductor material 6 is stated successively to be arranged from top to bottom；The first conductor material 1
It is connect with pulse dc power anode 2, the second conductor material 6 is connect with pulse dc power cathode 5；The insulated enclosure
Microchannel electrodeposition bath 10 is provided in circle 3, and the microchannel electrodeposition bath 10 is by material inlet, material outlet and one group or more
S type microchannel composition；The material inlet is connect with the entrance and exit of the microchannel of S type respectively with material outlet, i.e.,
The microchannel electrodeposition bath 10 is that material inlet, the microchannel of one group or more of S type and material outlet are sequentially connected with；The object
Material import is connect by materail tube 4 with material pot 8, and the material outlet is connect by discharge nozzle 9 with material pot 8.The material
Liquid circulation pump 7 is provided on materail tube 4 between import and material pot 8.The microchannel of the S type is that cross section is diameter 2
The semi-circular grooves of~20mm or cross section are the rectangular grooves of 2~20mm depth *, 2~20mm width.Described first leads
The material of body material 1 is selected from graphite or metal；The material of the second conductor material 6 is selected from graphite or metal.It is described exhausted
The material of edge sealing ring 3 includes the various ambroin or silicone insulation material for sealing attribute；The material of the insulated enclosure circle 3
Material includes polytetrafluoroethylene (PTFE) or polystyrene.Lead between the first conductor material 1, insulated enclosure circle 3 and the second conductor material 6
Bolt is crossed to fix.
Embodiment 1:TiN@Pt catalyst
The preparation of 1.TiN core nanoparticle
80mL dehydrated alcohol is added in Meng Shi wash bottle, 20mLTiCl is then added4.After ultrasonic (stirring) is uniform, lead to
Enter ammonia, until the sediment quantity of formation is not further added by；Ammonia is disconnected, after wash bottle is covered, vacuum oven is transferred to, 50
Vacuum drying evaporation solvent for 24 hours, obtains the ammino-complex solid of titanium in DEG C baking oven；
It takes 500mg complex solid to be put into quartz boat, is put into quartz ampoule stone furnace, be first passed through in High Purity Nitrogen displacement boiler tube
Air then passes to ammonium hydroxide and starts to warm up；In 10ml/min, heating rate is 5 DEG C/min for ammonia flow rate control；It is warming up to
800 DEG C then constant temperature nitrogenizes two hours at this temperature, then switches to high pure nitrogen and starts to cool down, takes after being cooled to room temperature
Out, with XRD determining, product obtained is the TiN (card number: JCPDS NO.38-1420) of pure face cube structure.
2. microchannel recycle stream dynamic formula pulse electrodeposition
Taking 20mL pulse liquid, (concentration is the H of 2.5g/L2PtCl6·6H2O, concentration is the polyvinylpyrrolidone of 6g/L, dense
The sulfuric acid that the sodium sulphate that degree is 0.1mol/L is 0.4mol/L with concentration) ultrasonic agitation 1h is mixed with 20gTiN, keep its mixing equal
Material pot 8 is added after even.DC power supply is connected to device by pulse dc power anode 2 and pulse dc power cathode 5 again
In, and when to set the time (Ton) that required pulse current is -150mA, pulse is primary be 0.003s with the pulse spacing each time
Between (Toff) be 0.03s pulse electrodeposition program as preparation.Microchannel used is half that cross section is diameter 11mm
Circular groove, selected insulation spacer are the gasket that polytetrafluoroethylene (PTFE) is processed into.Start liquid circulating pump 7 regulates suitable compacted
Dynamic speed is 1mL/min.Beginning circulation from material pot 8 extracts mixed liquor and is input to microchannel electrodeposition bath 10 from materail tube 4
In be ready for pulsed deposition experiment.After material is from the outflow of discharge nozzle 9, starting impulse program, among two pieces of conductor plates
Microchannel 10 carries out circulating pulse electrodeposition.After pulse protocol stopping, liquid whole in S type microchannel are arranged through discharge nozzle
After out, stop the work of peristaltic pump；TiN@Pt structure catalyst needed for will being after resulting materials washing, drying.
3. the structure and morphology of catalyst characterizes and performance test
(1) the structure and morphology characterization of catalyst:
Nitride nano particle is observed using transmission electron microscope (TEM) and deposits the pattern of the nitride nano particle of platinum
The average grain diameter of (Fig. 3), titanium nitride made from the present embodiment are 8~11nm, and particle diameter distribution is more uniform.From fig. 4, it can be seen that
The platinum of pulse electrodeposition method deposition does not form particle on titanium nitride surface, and utilizes high-resolution-ration transmission electric-lens figure can be clear
The lattice fringe for seeing Pt and titanium nitride, there is also apparent differences between two kinds of stripeds, it was demonstrated that Pt is with atomic layer level thickness
Rank deposition.The platinum carrying capacity that the result of icp analysis measures catalyst made from the present embodiment is 5.3wt%.
(2) cathodic oxygen reduction catalytic performance test:
Using three-electrode system, the catalyst with core-casing structure being collected into is coated on glass-carbon electrode, in oxygen saturation
0.1M HClO4In, with the speed of sweeping of 10mV/s, the electrode revolving speed of 1600r/min carries out linear voltammetric scan, as a result sees Fig. 4
Embodiment 2:TiNiN@Pt catalyst
1. the preparation of bimetallic nitridation NiTi (TiNiN) core nanoparticle:
In draught cupboard, 80mL ethyl alcohol is added in Meng Shi wash bottle, 20mL TiCl is then added4Solution and 1.697g
Nickel acetate tetrahydrate, stirring dissolve it sufficiently, and the atomic ratio of Ti and Ni are 19:1, other preparation flows are same as Example 1.
2. preparing TiNiN Pt using microchannel recycle stream dynamic formula pulse electrodeposition:
Except rectangular grooves that microchannel used is 10mm (depth) * 20mm (width), gasket used add for polystyrene
Work at gasket outside, remaining step is the same as embodiment 1.
Gained core-shell structure TiNiN@Pt catalytic oxygen reduction activity has been more than business Pt/C catalyst, as shown in Figure 4.
Embodiment 3:TiN@Pt/NCNT catalyst
1. the preparation that nitrogen-doped carbon nanometer pipe (NCNT) loads titanium nitride (TiN):
In draught cupboard, 80mL ethyl alcohol is added in Meng Shi wash bottle, 5mL TiCl is then added4Solution and 17.5g carbon
Nanotube, stirring mix them thoroughly, and it is 80% that carbon carrier, which accounts for substrate quality ratio,.Other processes with embodiment 1, resulting materials
Transmission electron microscope photo is shown in Fig. 5.
2. standby TiN Pt/NCNT is prepared using microchannel recycle stream dynamic formula pulse electrodeposition, in addition to following several points are different,
It is with embodiment 1:
(1) pulse liquid (tetraammineplatinum chloride, wherein Pt concentration 5g/L, sodium sulphate containing 0.1M, 0.125M sodium citrate)；
(2) pulse current is 100mA, and the admittance time is 0.3ms, turn-off time 1.5ms
The hydrogen reduction performance of catalyst made from the present embodiment is 3.9 times of business Pt/C catalyst.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (10)
1. a kind of microchannel recycle stream dynamic formula pulse electrodeposition device for being used to prepare platinum base catalyst with core-casing structure, feature exist
In, including the first conductor material (1), pulse dc power positive (2), insulated enclosure circle (3), materail tube (4), pulse direct current
Source cathode (5), the second conductor material (6), material pot (8) and discharge nozzle (9)；The first conductor material (1), insulated enclosure circle
(3) successively it is arranged from top to bottom with the second conductor material (6)；The first conductor material (1) and pulse dc power are positive (2)
Connection, the second conductor material (6) connect with pulse dc power cathode (5)；It is provided in the insulated enclosure circle (3) micro-
Channel electrodeposition bath (10), the microchannel electrodeposition bath (10) by material inlet, material outlet and one group or more S type it is micro-
Channel composition；The material inlet is connect with the entrance and exit of the microchannel of S type respectively with material outlet, i.e., the described microchannel
Electrodeposition bath (10) is that material inlet, the microchannel of one group or more of S type and material outlet are sequentially connected with；The material inlet is logical
It crosses materail tube (4) to connect with material pot (8), the material outlet is connect by discharge nozzle (9) with material pot (8).
2. being used to prepare the microchannel recycle stream dynamic formula pulse electrodeposition of platinum base catalyst with core-casing structure according to claim 1
Device, which is characterized in that be provided with liquid circulation pump (7) on the materail tube (4) between the material inlet and material pot (8).
3. being used to prepare the microchannel recycle stream dynamic formula pulse electrodeposition of platinum base catalyst with core-casing structure according to claim 1
Device, which is characterized in that the microchannel of the S type is the semi-circular grooves that cross section is 2 ~ 20 mm of diameter or cross section is
The rectangular grooves of 2 ~ 20 mm*, 2 ~ 20 mm.
4. being used to prepare the microchannel recycle stream dynamic formula pulse electrodeposition of platinum base catalyst with core-casing structure according to claim 1
Device, which is characterized in that the material of the first conductor material (1) is selected from graphite or metal；The second conductor material (6)
Material be selected from graphite or metal.
5. being used to prepare the microchannel recycle stream dynamic formula pulse electrodeposition of platinum base catalyst with core-casing structure according to claim 1
Device, which is characterized in that the material of the insulated enclosure circle (3) includes the various ambroin or silicone insulation for sealing attribute
Material；The material of the insulated enclosure circle (3) includes polytetrafluoroethylene (PTFE) or polystyrene.
6. being used to prepare the microchannel recycle stream dynamic formula pulse electrodeposition of platinum base catalyst with core-casing structure according to claim 1
Device, which is characterized in that pass through spiral shell between the first conductor material (1), insulated enclosure circle (3) and the second conductor material (6)
Bolt is fixed.
7. the application method of any one of claim 1 ~ 6 described device, which comprises the following steps:
S1: taking Pt precursor compound, surfactant and electrolyte dissolution in solvent, is made into pulse liquid A；
S2: taking core nano material that pulse liquid A is added makes it after mixing by processing such as ultrasonic method, stirrings, wiring solution-forming B；
S3: solution B is transferred in material pot 8, then pulse dc power positive (2) and pulse dc power cathode (5) are divided
It is not connected on electrochemical workstation, and sets pulse electrodeposition program as preparation；
S4: start liquid circulating pump (7) makes mixed liquid B be delivered to microchannel electricity via materail tube 4 with the flow velocity of 1 ~ 5L/min and sinks
Product pond (10), and material pot (8) are returned by discharge nozzle (9)；
S5: starting impulse program, the microchannel electrodeposition bath between the first conductor material (1) and the second conductor material (6)
(10) recycle stream dynamic formula pulse electrodeposition is carried out；
S6: after pulse protocol stopping, by liquid whole in microchannel electrodeposition bath (10) after discharge nozzle is discharged, stop solution
Body circulation pumps the work of (7)；
S7: will through pulse treated after pulse liquid is centrifuged, washed and dried be needed for Pt base catalyst with core-casing structure.
8. application method according to claim 6, which is characterized in that in step S1, the concentration of Pt precursor compound is 1
~ 5 g/L, the Pt precursor compound are H2PtCl6Or K2PtCl6；The concentration of the surfactant is 2 ~ 10 g/L,
The surfactant is polyvinylpyrrolidone；The sodium sulphate and concentration that the electrolyte is 0.1 ~ 0.5mol/L by concentration
It is formed for the sulfuric acid of 0.2 ~ 0.8mol/L；The solvent is water.
9. application method according to claim 6, which is characterized in that in step S2, the core nano material are as follows: TiN, WC
Or metal；The metal includes Pd or Au.
10. application method according to claim 6, which is characterized in that in step S3, the pulse protocol is pulse current
For -50mA ~ -800mA；Burst length is 0.003s ~ 0.03s, and each interpulse period is set as 0.01 ~ 1.0 s, pulse processed time
Number is 20000 ~ 80000 times.
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