CN107732260A - A kind of preparation method of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure - Google Patents
A kind of preparation method of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure Download PDFInfo
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- CN107732260A CN107732260A CN201710886110.6A CN201710886110A CN107732260A CN 107732260 A CN107732260 A CN 107732260A CN 201710886110 A CN201710886110 A CN 201710886110A CN 107732260 A CN107732260 A CN 107732260A
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- doping
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- nickel bimetal
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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
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group 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
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Abstract
The invention discloses a kind of preparation method of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure, this method comprises the following steps：By glucose, urea, nickel nitrate and platinum acid chloride solution are mixed in beaker, are configured to the aqueous solution, drying, are then calcined under nitrogen atmosphere in high temperature process furnances, gained sample is ground into no granulated powder, so as to obtain the platinum nickel bimetal catalyst of N doping.The platinum nickel bimetal catalyst of N doping prepared by the present invention is in potassium hydroxide solution, there is remarkable electrocatalytic oxidation activity to ethanol, good stability, and preparation cost is cheap, is a kind of novel high-performance catalyst for Direct Ethanol Fuel Cell anode.
Description
Technical field
The invention belongs to fuel cell catalyst technical field, the N doping platinum nickel for specifically providing a kind of cubic structure is double
The preparation method of metal ethanol oxidation catalyst.
Background technology
At present, anode and cathode catalysis are mainly used as using precious metal material in the research and application of Direct Ethanol Fuel Cell
Agent, it is not high yet with platinum catalyst existence and stability, the problems such as being easily poisoned and be expensive, it is commercialized seriously to hinder its
Development, therefore researchers are compound or in a manner of doping mix minimal amount of platinum by platinum and base metal, so as to reach
Cost can be reduced, and can improves the purpose of catalyst activity, and this also turns into the commercial applications of platinum based catalyst can
Energy.
Nickel electrode uses extensively in ethanol electrocatalytic oxidation, and in non-precious metal catalyst, Ni metals are to ethanol oxygen
Change shows very high electro catalytic activity, such as Ni-Co alloys, nickel nanowire, and wherein nickel nanowire is to ethanol electrocatalytic oxidation
Show good performance.Xie et al. is prepared for nickel and multi-walled carbon nanotube composite catalyst using the method for electro-deposition, nickel
Average grain diameter only has 7.2nm, and is evenly distributed on multi-walled carbon nanotube.(Journal of Materials
Chemistry A, 2013,1 (6)：2104-2109) Tarasevich et al. have studied RuNi/C catalyst, and use nickel oxide
To modify Ru, when Ru and Ni optimal proportion is 70: 30, good electrocatalysis characteristic is shown.When Ru and Ni compositions occur
During change, the oxidation susceptibility of ethanol on a catalyst is also changed.(Electrochemistry communications,
2005,7 (2)：141-146) it is possible thereby to prove, nickel-base catalyst has good catalytic performance to ethanol electrocatalytic oxidation.
The appearance and size of catalyst has a great impact to catalytic performance.For example, Jia et al. pass through it is a kind of simple and effective
Method has synthesized Ni-Fe layered double-hydroxides (LDH) nanometer sheet and layering Ni-Fe LDH@MnO2Ball carrys out electrocatalytic oxidation second
Alcohol.Compared with Ni-Fe LDH nanometer sheets, LDH@MnO2Microballoon shows excellent catalytic activity and to the durable of ethanol electrooxidation
Property.(RSC Advances, 2015,5 (101)：83314-83319) Tian et al. by difference pulse electric current electro-deposition method into
Manufactured the Ni-Cu alloy nanowire arrays of high-sequential work(, and the nano wire in array is uniform, and good separation is simultaneously
It is and parallel to each other.The performance of ethanol electrooxidation is controlled by changing the Cu contents in Ni-Cu alloys, and Ni-Cu alloys are received
Rice noodles electrode shows stability more more preferable than pure Ni.(Nanotechnology, 2008,19 (21)：215711)
The content of the invention
It is an object of the invention to provide a kind of system of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure
Preparation Method, its feature comprise the following steps：By 1.0~3.0g of glucose, 0.2~1.0g of urea, 0.1~0.5g of nickel nitrate and chlorine
0.1~0.7mL of platinic acid solution is mixedly configured into the aqueous solution, then in 100~120 DEG C of dry 10~12h, is subsequently placed into and persistently leads to
Enter and calcined in the high temperature process furnances of nitrogen, heating rate is 6~10 DEG C/min, and calcining heat is 700~1200 DEG C, insulation
Time is 1~6h, and gained sample is ground to no granulated powder after calcining, produces the platinum nickel bimetal catalyst of N doping.
Beneficial effects of the present invention are：
The invention provides a kind of preparation method of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure, sheet
The use of glucose is carbon source in method, aboundresources, price is excellent honest and clean, and can be provided after glucose carbonization high specific surface area and
More avtive spots；N doping provides abundant nitrogen functional group and more catalytic sites for catalyst, and reduces and urge
The particle size of agent；The structure that platinum amount by changing incorporation can effectively regulate and control catalyst is cubic.These knots
Structure feature can effectively improve the performance of Catalysts for Electrocatalytic Oxidation ethanol, include the current density of superelevation, good circulation
Stability and low take-off potential.
Brief description of the drawings
Fig. 1 is the HRTEM figures of the platinum nickel bimetal catalyst of N doping prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD of the platinum nickel bimetal catalyst of N doping prepared by the embodiment of the present invention 1；
Fig. 3 is the cyclic voltammetry curve figure of the platinum nickel bimetal catalyst of N doping prepared by the embodiment of the present invention 1.
Embodiment
Embodiment is set forth below to be further described the present invention, but the invention is not restricted to following embodiments, is not taking off
Under scope from the front and rear objective, change is included in the technical scope of the present invention.
Embodiment 1
Comprise the following steps that：
(1) under room temperature condition, by 2g glucose, 0.8g urea, 0.3g nickel nitrates and 0.5mL concentration are 7.91mg/mL's
Platinum acid chloride solution is mixed in beaker, adds 50mL deionized waters, is then placed in baking oven and is dried 12h；
(2) under room temperature condition, the sample of drying is moved in graphite cuvette, is then placed in vacuum tube furnace and is calcined,
Heating rate is 5 DEG C/min, 900 DEG C of calcining heat, is incubated duration 3h；
(3) sample after calcining is ground to no granulated powder, produces the platinum nickel bimetal catalyst of N doping.Fig. 1
For the HRTEM figures of the platinum nickel bimetal catalyst of the N doping of preparation, show that catalyst is in cubic structure in figure, and granular size
It is homogeneous, it is evenly distributed.Fig. 2 is the platinum nickel bimetal catalyst XRD of the N doping prepared, and as can be seen from the figure platinum and nickel are equal
Successfully load in catalyst, and be all in metal simple-substance state.Fig. 3 is that the platinum nickel bimetal catalyst of the N doping prepared exists
Cyclic voltammetry curve figure in 0.1mol/mL sodium hydroxide+0.1mol/mL ethanol solutions, as can be seen from the figure platinum nickel is double
The take-off potential of metallic catalyst is small, and current density is high, and has good cyclical stability.
Embodiment 2
It is same as Example 1, except the dosage of platinum acid chloride solution is changed into 0.3mL.Thus the catalyst structure pattern prepared
Irregularly, it is scattered uneven, and relative to embodiment 1, current density is relatively low.
Embodiment 3
It is same as Example 1, except the dosage of platinum acid chloride solution is changed into 0.1mL.Thus the catalyst prepared is relative to reality
Example 1 is applied, take-off potential is higher, particle size increase.
The explanation of above example is only intended to help the method and core concept for understanding the present invention, is not departing from the present invention
Principle under the improvement and modification that carry out, all should be included within the scope of the invention.
Claims (5)
- A kind of 1. preparation method of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure, it is characterised in that：Room temperature Under the conditions of, glucose, urea, nickel nitrate and platinum acid chloride solution are mixedly configured into the aqueous solution, dries, dried sample is put Enter in high temperature process furnances and calcined, you can obtain platinum nickel bimetal catalyst.
- A kind of 2. preparation side of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure as claimed in claim 1 Method, it is characterised in that the dosage of described glucose, urea, nickel nitrate and platinum acid chloride solution is respectively 1.0~3.0g, 0.2~ 1.0g, 0.1~0.5g and 0.1~0.7mL.
- A kind of 3. preparation side of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure as claimed in claim 1 Method, it is characterised in that the drying condition is：100~120 DEG C of drying temperature, 10~12h of drying time.
- A kind of 4. preparation side of the N doping platinum nickel bimetal ethanol oxidation catalyst of cubic structure as claimed in claim 1 Method, the calcination process include following condition：Heating rate is 6~10 DEG C/min, and calcining heat is 700~1200 DEG C, insulation Time is 1~6h.
- 5. N doping platinum nickel bimetal ethanol oxidation catalyst prepared by the preparation method as described in claims 1~4, in alkali Property environment in electrocatalytic oxidation ethanol current density it is high low with take-off potential.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659567A (en) * | 2018-11-30 | 2019-04-19 | 天津大学 | The sugared cell anode catalyst and preparation method and application of nickel and cobalt containing nitrogen |
| CN114101696A (en) * | 2021-09-16 | 2022-03-01 | 北京航空航天大学 | Phosphorus-doped platinum-nickel nanowire and preparation method and application thereof |
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| JP2011016125A (en) * | 2009-06-11 | 2011-01-27 | Honda Motor Co Ltd | Alloy catalyst for oxidation-reduction reaction |
| CN103157494A (en) * | 2013-04-01 | 2013-06-19 | 河北师范大学 | Method of synthesizing Pt-Ni catalyst material by hydrothermal method |
| CN103816894A (en) * | 2014-02-17 | 2014-05-28 | 武汉科技大学 | Pt-Ru alloy nano electro-catalyst having doped graphene carrier and preparation method thereof |
| CN104353480A (en) * | 2014-09-26 | 2015-02-18 | 广西师范大学 | Three-dimensional nitrogen-doped graphene platinoid-loaded composite electro-catalyst and preparation method thereof |
| CN106058274A (en) * | 2016-06-20 | 2016-10-26 | 三峡大学 | PtCu electric catalyst for fuel battery, preparation method and application thereof |
| CN106450350A (en) * | 2016-10-20 | 2017-02-22 | 绍兴文理学院 | Method for synthesizing platinum nano cubic block |
-
2017
- 2017-09-26 CN CN201710886110.6A patent/CN107732260A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011016125A (en) * | 2009-06-11 | 2011-01-27 | Honda Motor Co Ltd | Alloy catalyst for oxidation-reduction reaction |
| CN103157494A (en) * | 2013-04-01 | 2013-06-19 | 河北师范大学 | Method of synthesizing Pt-Ni catalyst material by hydrothermal method |
| CN103816894A (en) * | 2014-02-17 | 2014-05-28 | 武汉科技大学 | Pt-Ru alloy nano electro-catalyst having doped graphene carrier and preparation method thereof |
| CN104353480A (en) * | 2014-09-26 | 2015-02-18 | 广西师范大学 | Three-dimensional nitrogen-doped graphene platinoid-loaded composite electro-catalyst and preparation method thereof |
| CN106058274A (en) * | 2016-06-20 | 2016-10-26 | 三峡大学 | PtCu electric catalyst for fuel battery, preparation method and application thereof |
| CN106450350A (en) * | 2016-10-20 | 2017-02-22 | 绍兴文理学院 | Method for synthesizing platinum nano cubic block |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659567A (en) * | 2018-11-30 | 2019-04-19 | 天津大学 | The sugared cell anode catalyst and preparation method and application of nickel and cobalt containing nitrogen |
| CN114101696A (en) * | 2021-09-16 | 2022-03-01 | 北京航空航天大学 | Phosphorus-doped platinum-nickel nanowire and preparation method and application thereof |
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