CN108878908A - A kind of novel method for preparing catalyst with core-casing structure - Google Patents
A kind of novel method for preparing catalyst with core-casing structure Download PDFInfo
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- CN108878908A CN108878908A CN201810743366.6A CN201810743366A CN108878908A CN 108878908 A CN108878908 A CN 108878908A CN 201810743366 A CN201810743366 A CN 201810743366A CN 108878908 A CN108878908 A CN 108878908A
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- core
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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
- H01M4/9075—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to catalyst with core-casing structure technical fields, and in particular to a kind of novel method for preparing catalyst with core-casing structure is different from the prior art, and the present invention is using microreactor and in the microreactor：It prepares carbon-supported metal core, using polyol process shell metal, and makes the shell metal and the carbon-supported metal nuclear reaction that nucleocapsid catalyst be made.The method preparation efficiency provided by the invention for preparing catalyst with core-casing structure is higher, and the raw material needed is less, easy to operate.
Description
Technical field
The invention belongs to catalyst with core-casing structure technical fields, and in particular to a kind of novel catalyst with core-casing structure for preparing
Method.
Background technique
Fuel cell is a kind of power generator that will be present in fuel and be converted into electric energy with the chemical energy in oxidant.
Fuel and air are fed separately to fuel cell, and then output electric energy applies it in existing equipment, such as military affairs, space, hair
The fields such as power plant and motor vehicle, mobile device, residential households, wherein it is most important to push this fuel cells convert to go out electric energy
One link is exactly catalyst, and catalyst can make the output electric energy of raw material rapidly and efficiently.Urging applied to fuel cell at present
Agent is catalyst with core-casing structure.
A kind of existing nucleocapsid catalyst of carbon-supported nano copper-nickel alloy core-noble metal shell of patent and preparation method thereof (application
Number CN201510002591.0) provide nucleocapsid catalyst and its preparation of a kind of carbon-supported nano copper-nickel alloy core-noble metal shell
Method, belongs to fuel cell and energy saving electrolysis field, the present invention using conductive carbon material as carrier, with anti-corrosion, alloying level is high
Base metal CuNi alloy be kernel, noble metal (M：The alloy that Pt, Pd, Ru, Ir, Rh one or both of work as) for shell
Prepare nuclear shell on carbon metallic catalyst.Its preparation step is：The carbon for being impregnated with cupro-nickel salt is heat-treated under reducing atmosphere
(300~1000 DEG C) obtain CuNi/C, this CuNi/C is flowed back in the ethylene glycol for having precious metal salt and PVP reduction, obtain
CuNi@M/C nucleocapsid catalyst.The method for preparing catalyst with core-casing structure uses reduction of ethylene glycol, and is preparing shell
When structure use surfactant, such as polyvinylpyrrolidone, the preparation method is more complicated, and need raw material compared with
It is more.
The manufacturing method (application number CN201580041409.0) of existing patent nucleocapsid catalyst discloses a kind of nucleocapsid and urges
The manufacturing method of agent, with the high nucleocapsid catalyst of short time manufacture platinum mass activity.The manufacturing method of the nucleocapsid catalyst
Be have core containing palladium and containing platinum and be coated the core shell nucleocapsid catalyst manufacturing method, preparation make in grain containing palladium
The surface of son is coated copper made of copper and is coated copper made of the dispersion of particle containing palladium coating particle dispersion containing palladium, platiniferous solion
And microreactor, by the way that the coating particle dispersion containing palladium of the copper and the platiniferous solion are mixed in the microreactor
It closes, the copper that the copper is coated the particle surface containing palladium is replaced into platinum, forms the shell.This method is improved by using microreactor
Prepare the efficiency of nucleocapsid catalyst, but the nucleocapsid preparation side that is specifically replaced using the copper that will overlay on palladium surface by platinum
Method, relative response method is more complicated, and microreactor is only applied to prepare the process of shell, therefore improves on preparation efficiency
Effect be not obvious.
Therefore according to problems of the prior art, it is simpler that the present invention provides a kind of preparation method, preparation efficiency
The method of more efficient catalyst with core-casing structure.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention adopts the following technical scheme that：
A method of catalyst with core-casing structure being prepared, using microreactor and in the microreactor：Prepare carbon load
Metal core, using polyol process shell metal, then make the shell metal and the carbon-supported metal nuclear reaction that core-shell structure be made
Catalyst.
Preferably, specifically comprise the following steps：
S1, the mixed aqueous solution for configuring metal salt and citric acid obtain the solution a that concentration is 0.01-0.1g/ml；
S2, the aqueous alkali b that configuration concentration is 5g/L-10g/L；
S3, the slurry c that configuration concentration is 0.1g/L-1g/L；
S4, the solution a, the aqueous alkali b and the slurry c are injected in microreactor, in the microreactor
After middle hybrid reaction, the mixed liquor of the solution a, the aqueous alkali b and slurry c are collected, and sodium borohydride is added, is starched
Liquid d；
S5, the slurries d is filtered using positive press filtration device, then filtrate is washed with water, specifically may be used
Filtrate is washed using ultrapure water with selection, it is finally dry using vacuum oven, obtain carbon-supported metal core e；
S6, it disperses carbon-supported metal core e in polyhydric alcohol solutions, while the alcoholic solution of metal salt is added, obtain solution f；
S7, KOH ethylene glycol solution is added dropwise in solution f, obtains solution g；
S8, solution g is injected into T-type microchannel, controls reaction temperature using temperature control system, it is anti-to after reaction, collect
Product is answered, and is successively filtered, washs, dries and grinds, finally obtains catalyst with core-casing structure.
Preferably, the molar ratio of metal salt described in the S1 and the citric acid is 1:1-1:7.
Preferably, in the S2, specifically used KOH, NaOH, ethamine is a kind of in triethylamine and ammonium hydroxide to prepare aqueous alkali
b。
Preferably, in the S3, it is described in 0.1g/L-1g/L that concentration, which is made, in carbon black dispersion by specifically used mid-frequency ultrasonic
Slurry c, in 30-60min, the carbon black is one in carbon black XC-72, carbon black AC30 and carbon black ECP600 for ultrasonic time control
Kind is several.
Preferably, in the S4, specifically use one of syringe pump, plunger pump, diaphragm pump and peristaltic pump with 0.1-
The flow velocity of 20mL/min, which injects the solution a, the aqueous alkali b and the slurry c in microreactor, carries out mixing and anti-
It answers, and controlling reaction temperature is 10-25 DEG C, reaction time 10-50min；In the obtained slurries d, sodium borohydride
It is 1 with metal molar ratio：1-5：1.
Preferably, in the S5, pressure when the specifically used positive press filtration device filters is 1kpa, and filter sizes are
It 0.2 μm, after filtering, is washed with water 4-5 times, then controls in the vacuum oven that drying temperature is 60 DEG C
Dry 12h, obtains the carbon-supported metal core e after drying.
Preferably, alcohol used in the alcoholic solution for the metal salt being added in the S6 carries gold with for dispersing the carbon
It is identical to belong to the polyalcohol that core e is used, wherein the concentration of the alcoholic solution of the metal salt is 0.01g/L-10g/L, finally makes described
The molar ratio of shell and core in solution f is 0.5-2.
Preferably, in the S7, the mass concentration of the solution g is 1%-5%, PH 8-10.
Preferably, in the S8, specific reaction temperature is 90-130 DEG C.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention is to adapt to mixing and reaction using microreactor in the whole process for preparing catalyst with core-casing structure,
In the step of synthesizing shell, conventional method needs prolonged reduction, and the present invention can be greatly reduced also using microreactor
The former time, while heat transfer, mass transfer problem that amplification preparation occurs are solved, greatly facilitate the catalysis of industrialized production core-shell structure
Agent；The present invention has also made on the composition for prepare raw material and being correspondingly improved：It is not added with surfactant, saves and prepares raw material
While, last preparation effect is not influenced；In the present invention, the applicable citric acid of the present invention is made unlike the prior art
In order that the excessive effect of mechanism carbon-supported metal core, the quality that catalyst with core-casing structure is prepared is improved.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the Electron microscope figure of the embodiment of the present invention two,
Fig. 2 is the Electron microscope figure of comparative example of the present invention,
Fig. 3 is the platinoid nucleocapsid catalyst XRD characterization figure of the embodiment of the present invention two and comparative example preparation；
1 represents embodiment two；2 represent comparative example 1.
Specific embodiment
The preferred embodiment of the present invention is described with reference to the accompanying drawing：
Embodiment one
A method of catalyst with core-casing structure being prepared, using microreactor and in the microreactor：Prepare carbon load
Metal core, using polyol process shell metal, then make the shell metal and the carbon-supported metal nuclear reaction that nucleocapsid catalysis be made
Agent.
Specifically comprise the following steps：
S1, according to the molar ratio of metal salt and citric acid be 1:1-1:The mixed aqueous solution of 7 configuration metal salts and citric acid,
Obtain the solution a that concentration is 0.01-0.1g/ml；
S2, using KOH, NaOH, ethamine, a kind of aqueous alkali that configuration concentration is 5g/L-10g/L in triethylamine and ammonium hydroxide
b；
S3, one or more of carbon black XC-72, carbon black AC30 and carbon black ECP600 are dispersed to be made using mid-frequency ultrasonic
Concentration is the slurry c of 0.1g/L-1g/L, and the ultrasonic time controls in 30-60min；
S4, use one of syringe pump, plunger pump, diaphragm pump and peristaltic pump will be described with the flow velocity of 0.1-20mL/min
Solution a, the aqueous alkali b and the slurry c, which inject in microreactor, to be mixed and is reacted, and is controlled reaction temperature and be
10-25 DEG C, reaction time 10-50min, the mixed liquor of the solution a, the aqueous alkali b and slurry c are then collected, and
Sodium borohydride is added and obtains slurries d, in the obtained slurries d, sodium borohydride and metal molar ratio are 1：1-5：1；
S5, the slurries d is filtered using positive press filtration device, and controlling pressure is 1kpa, the filter of positive press filtration device
Membrane aperture is 0.2 μm, after filtering, is washed with water 4-5 times, and the vacuum for being 60 DEG C in drying temperature is then controlled
Dry 12h, obtains carbon-supported metal core e in drying box；
S6, it disperses carbon-supported metal core e in polyhydric alcohol solutions, while the alcoholic solution of metal salt is added, obtain solution f,
Alcohol used in the alcoholic solution for the metal salt being added is identical as dispersing the polyalcohol that the carbon-supported metal core e is used,
Wherein the concentration of the alcoholic solution of the metal salt is 0.01g/L-10g/L, finally makes the molar ratio of the shell and core in the solution f
For 0.5-2；
S7, KOH ethylene glycol solution being added dropwise in solution f, obtains solution g, the mass concentration of the solution g is 1%-5%,
PH is 8-10；
S8, solution g is injected into T-type microchannel, using temperature control system control reaction temperature between 90-130 DEG C, wait react
After, collecting reaction product, and be successively filtered, wash, dry and grind, finally obtain catalyst with core-casing structure.
Embodiment two
S1, weighing 0.109g cupric sulfate pentahydrate and 0.263g citric acid are dissolved in 50mL water and obtain solution a respectively；
S2,0.270gKOH is weighed again be dissolved in 30mL water and obtain aqueous alkali b；
S3, by 0.12g carbon black AC30 ultrasonic disperse in 100mL water, ultrasound obtains slurry until carbon black is without fine particle
c；
S4, solution a and slurry c is entered in microreactor with flow velocity 2.5mL/min and 5mL/min respectively, then with flow velocity
For the aqueous alkali b microring array of 1.5mL/min, controls reaction temperature and the time is respectively 20 DEG C and 15min, solution adds after reaction
Enter 40mg sodium borohydride and obtains solution d；
S5, positive press filtration device filtering solution d, then water washing 4-5 times, finally using vacuum oven control drying are used
Carbon-supported metal core e is obtained after temperature 60 C vacuum drying 12h, wherein the copper-loaded nano particle of carbon, wherein copper is as core；
S6, by carbon-supported metal core e ultrasonic disperse in 50mL ethylene glycol, be added concentration 0.02g/g chloroplatinic acid ethylene glycol it is molten
Liquid 7.06g continues ultrasound 30min, obtains solution f
S7,5%KOH ethylene glycol solution is then added dropwise into solution f, adjusting PH is 8-9, and ultrasound is to slurry without tiny
Grain, obtains solution g；
S8, solution g is entered into microchannel with flow velocity 7mL/min, controlled at 100 DEG C, collecting reaction product, product is passed through
Filtering, water washing 5-6 times, 80 DEG C at a temperature of be dried in vacuo 12h, obtain nucleocapsid platinoid catalyst with core-casing structure.
Comparative example
S1, weighing 0.109g cupric sulfate pentahydrate and 0.263g citric acid are dissolved in 50mL water and obtain solution a respectively；
S2,0.270gKOH is weighed again be dissolved in 30mL water and obtain aqueous alkali b；
S3, by 0.12g carbon black AC30 ultrasonic disperse in 100mL water, ultrasound obtains slurry until carbon black is without fine particle
c；
S4,1.5h, mixing speed 500r/min is mixed in solution a and slurry c, aqueous alkali b, reaction is then added dropwise
20 DEG C of reduction 15min of 40mg sodium borohydride are added in solution afterwards, obtain solution d,
S5, solution d is filtered, water washing 4-5 times, obtains carbon-supported metal core e after 60 DEG C of vacuum drying 12h, wherein carbon carries
Copper nano particles, wherein copper is as core；
S6, by carbon-supported metal core e ultrasonic disperse in 50mL ethylene glycol, be added concentration 0.02g/g chloroplatinic acid ethylene glycol it is molten
Liquid continues ultrasound 30min, obtains solution f；
S7,5%KOH ethylene glycol solution is added dropwise into solution f, adjusting PH is 8-9, and ultrasound, without fine particle, is obtained to slurry
To solution g；
S8, solution g is reacted into 4h under conditions of 100 DEG C of oil bath, collecting reaction product, product is through filtering, water washing 5-6
Secondary, 80 DEG C of vacuum drying 12h obtain nucleocapsid platinoid catalyst with core-casing structure.
Above-described embodiment two is recorded respectively and incorporation time, recovery time and the finally prepd core-shell structure of comparative example are urged
The electro-chemical activity of agent, the results are shown in Table 1 for record：
Table 1
The method provided by the invention for preparing catalyst with core-casing structure is either preceding it can be seen from the data in table 1
The mixing of phase or the reduction in later period, required time are far smaller than comparative example, comparative example, that is, prior art preparation side
Method, and also had using the activity of the catalyst with core-casing structure of the method preparation provided by the invention for preparing catalyst with core-casing structure
It is improved.
These are only the preferred embodiment of the present invention, is not limited to invent, although right with reference to the foregoing embodiments
The detailed description that the present invention carries out for those skilled in the art still can be to recorded in foregoing embodiments
Technical solution modify, or equivalent exchange is carried out to part of technical characteristic.It is all in the spirit and principles in the present invention
Within, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method for preparing catalyst with core-casing structure, which is characterized in that using microreactor and in the microreactor：
It prepares carbon-supported metal core, using polyol process shell metal, is then made the shell metal and the carbon-supported metal nuclear reaction
Catalyst with core-casing structure.
2. a kind of method for preparing catalyst with core-casing structure according to claim 1, which is characterized in that specifically include as follows
Step：
S1, the mixed aqueous solution for configuring metal salt and citric acid obtain the solution a that concentration is 0.01-0.1g/ml；
S2, the aqueous alkali b that configuration concentration is 5g/L-10g/L；
S3, the slurry c that configuration concentration is 0.1g/L-1g/L；
S4, the solution a, the aqueous alkali b and the slurry c are injected in microreactor, is mixed in the microreactor
After closing reaction, the mixed liquor of the solution a, the aqueous alkali b and slurry c is collected, and sodium borohydride is added, obtain slurries d；
S5, the slurries d is filtered using positive press filtration device, then filtrate is washed with water, finally using true
Empty drying box is dry, obtains carbon-supported metal core e；
S6, it disperses carbon-supported metal core e in polyhydric alcohol solutions, while the alcoholic solution of metal salt is added, obtain solution f；
S7, KOH ethylene glycol solution is added dropwise in solution f, obtains solution g；
S8, solution g is injected into T-type microchannel, controls reaction temperature using temperature control system, produced to after reaction, collect reaction
Object, and be successively filtered, wash, dry and grind, finally obtain catalyst with core-casing structure.
3. a kind of method for preparing catalyst with core-casing structure according to claim 2, which is characterized in that described in the S1
The molar ratio of metal salt and the citric acid is 1:1-1:7.
4. a kind of method for preparing catalyst with core-casing structure according to claim 2, which is characterized in that in the S2, tool
Body uses KOH, NaOH, and ethamine is a kind of in triethylamine and ammonium hydroxide to prepare aqueous alkali b.
5. a kind of method for preparing catalyst with core-casing structure according to claim 2, which is characterized in that in the S3, tool
Using mid-frequency ultrasonic the slurry c that concentration is 0.1g/L-1g/L is made in carbon black dispersion by body, and the ultrasonic time controls in 30-
60min, the carbon black are one or more of carbon black XC-72, carbon black AC30 and carbon black ECP600.
6. a kind of method for preparing catalyst with core-casing structure according to claim 2, which is characterized in that in the S4, tool
Body uses one of syringe pump, plunger pump, diaphragm pump and peristaltic pump with the flow velocity of 0.1-20mL/min by the solution a, institute
It states in aqueous alkali b and slurry c injection microreactor and is mixed and reacted, and controlling reaction temperature is 10-25 DEG C,
Reaction time is 10-50min；In the obtained slurries d, sodium borohydride and metal molar ratio are 1：1-5：1.
7. a kind of method for preparing catalyst with core-casing structure according to claim 2, which is characterized in that in the S5, tool
Pressure when body is filtered using the positive press filtration device is 1kpa, and filter sizes are 0.2 μm, after filtering, utilizes washing
It washs 4-5 times, then controls the dry 12h in the vacuum oven that drying temperature is 60 DEG C, obtain after drying described
Carbon-supported metal core e.
8. a kind of method for preparing catalyst with core-casing structure according to claim 2, which is characterized in that be added in the S6
The metal salt alcoholic solution used in alcohol it is identical as dispersing the polyalcohol that the carbon-supported metal core e is used, wherein
The concentration of the alcoholic solution of the metal salt is 0.01g/L-10g/L, finally makes the molar ratio of the shell and core in the solution f
0.5-2。
9. a kind of method for preparing catalyst with core-casing structure according to claim 2, which is characterized in that in the S7, institute
The mass concentration for stating solution g is 1%-5%, PH 8-10.
10. a kind of method for preparing catalyst with core-casing structure according to claim 2, which is characterized in that in the S8, tool
The reaction temperature of body is 90-130 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102088091A (en) * | 2010-12-17 | 2011-06-08 | 北京化工大学 | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof |
| CN104475126A (en) * | 2014-12-11 | 2015-04-01 | 北京化工大学 | Carbon-supported core-shell type platinum cobalt-platinum catalyst for fuel cells and preparation method for carbon-supported core-shell type platinum cobalt-platinum catalyst |
| CN106660014A (en) * | 2014-07-31 | 2017-05-10 | 丰田自动车株式会社 | Method for producing core-shell catalyst |
-
2018
- 2018-07-09 CN CN201810743366.6A patent/CN108878908A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102088091A (en) * | 2010-12-17 | 2011-06-08 | 北京化工大学 | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof |
| CN106660014A (en) * | 2014-07-31 | 2017-05-10 | 丰田自动车株式会社 | Method for producing core-shell catalyst |
| CN104475126A (en) * | 2014-12-11 | 2015-04-01 | 北京化工大学 | Carbon-supported core-shell type platinum cobalt-platinum catalyst for fuel cells and preparation method for carbon-supported core-shell type platinum cobalt-platinum catalyst |
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Application publication date: 20181123 |