CN108598496A - A kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity - Google Patents
A kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity Download PDFInfo
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- CN108598496A CN108598496A CN201810349293.2A CN201810349293A CN108598496A CN 108598496 A CN108598496 A CN 108598496A CN 201810349293 A CN201810349293 A CN 201810349293A CN 108598496 A CN108598496 A CN 108598496A
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- platinum
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- high activity
- fuel battery
- anode catalyst
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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
- H01M4/88—Processes of manufacture
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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
-
- 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
Abstract
The present invention relates to a kind of preparation methods of the platinum bismuth alloy fuel battery anode catalyst of high activity, include the following steps：(1) bismuth source is dissolved in reproducibility solvent, platinum source and stabilizer is then added, stirs and evenly mixs；(2) activated carbon powder is added in the mixed solution of step (1), is uniformly dispersed；(3) mixed solution of step (2) is passed through nitrogen deoxygenation, heats later and carries out condensing reflux；(4) after the cooling of step (3) mixed solution, filtering and washing is carried out, is finally dried to get to product.Compared with prior art, the present invention provides the preparation method that a kind of simple carbon of step carries PtBi alloys, simplify reaction step, obtained the Pt with alloy phase2Bi1Nano-particle, Pt, Bi two-phase do not detach, and can be effectively formed alloy phase nano-particle, significantly improve electrocatalytic oxidation activity of the Pt sills to ethyl alcohol.
Description
Technical field
The invention belongs to nanometer electrical catalyst preparation fields, and in particular to a kind of platinum bismuth alloy fuel cell sun of high activity
The preparation method of electrode catalyst.
Background technology
Direct Ethanol Fuel Cell is with alcohol fuel is nontoxic, theoretical energy density is high and alcohol fuel cell has
The characteristics of lower operating temperature, and ethyl alcohol can be obtained by the modes such as such as fermentation, ethylene aquation, and the source of fuel is wide
It is general, therefore be a kind of extremely potential renewable energy transfer device.It will to the correlative study of fuel-cell catalyst
The strong development for pushing Direct Ethanol Fuel Cell.Studies have shown that the electroxidation of ethyl alcohol is divided into the paths C1 and the paths C2, the paths C1
It is related to 12 electron reactions, ethyl alcohol is CO by CO intermediate complete oxidations2Or carbonate；The C-C keys of the paths C2 ethyl alcohol do not have
It is interrupted, is related to 4 or 2 electron reactions.C1 approach is oxidation of ethanol since transfer electron number is more, oxidation is thorough
Desirable route.Composition by improving Pt base fuel battery catalyst can effectively improve the selectivity of response path to carry
The electrocatalytic oxidation property and stability of high ethano.
Bimetallic alloy type nanocatalyst is more and more applied to fuel-cell catalyst field.Wherein, Bi elements
The special electronic effect generated to precious metal material can greatly enhance catalytic activity of the material to oxidation of ethanol itself.Research
Show in the substrate of Pt to can be changed Bi elements after surface modification the response path of alcohols electrocatalytic oxidation, therefore makes
A kind of standby PtBi alloy-types catalyst is a kind of available strategy improving material catalytic activity and stability.Bi elements, which introduce, to be generated
The catalytic activity significantly increased, mainly since Bi elements change the d having electronic states of base material, while promoting OHadObject
The formation of kind, to change the catalytic activity and selectivity of reaction, but NaBH traditional at present4Caused by quick reduction method meeting
Pt, Bi two-phase laminated flow cannot be effectively formed alloy phase nano-particle.
Invention content
The purpose of the present invention is exactly to solve the above-mentioned problems and PtBi alloy nanoparticles can be reliably formed by providing one kind
Son and to Direct Ethanol Fuel Cell it is anode-catalyzed have be obviously improved the Pt of effect2Bi1Alloy fuel cell anode catalyst
Preparation method.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity, includes the following steps：
(1) bismuth source is dissolved in reproducibility solvent, platinum source and stabilizer is then added, stirs and evenly mixs；
(2) activated carbon powder is added in the mixed solution of step (1), is uniformly dispersed；
(3) mixed solution of step (2) is passed through nitrogen deoxygenation, heats later and carries out condensing reflux；
(4) after the cooling of step (3) mixed solution, filtering and washing is carried out, is finally dried to get to product.
Further, the bismuth source described in step (1) is BiCl3, the platinum source is K2PtCl4, wherein bismuth element and platinum
The molar ratio of element is 1：2.
Further, the reproducibility solvent described in step (1) is ethylene glycol.
Further, the stabilizer described in step (1) is trisodium citrate.
Further, the activated carbon powder described in step (2) is Vulcan XC-72R activated carbon powders.
Further, step (2) carries out ultrasonic disperse after activated carbon powder is added.
Further, step (3) is heated to 180 DEG C of condensing reflux 3h under nitrogen atmosphere.
Further, step (4) uses milli-Q water for several times, in 60 DEG C of dry 12h in vacuum drying chamber.
Preparation method of the present invention uses ethylene glycol thermal reduction, with K2PtCl4、BiCl3For presoma, trisodium citrate is
Stabilizer, while Vulcan XC-72R activity carbon carriers are added, it will be before Pt, Bi by one-step method using the reproducibility of ethylene glycol
Drive the nano-particle that body is reduced to alloy phase, i.e. Pt2Bi1Alloy.Ethylene glycol is a kind of reducing agent that reproducibility is weaker, in high temperature
Under the conditions of its reproducibility be remarkably reinforced, can by Bi restore and with Pt formed alloy, another aspect trisodium citrate can be with presoma
It forms complex compound and generates certain steric effect, inhibit the growth of the particle in reduction process, finally obtain well dispersed, grain size
Properly, and to the electrocatalytic oxidation of ethyl alcohol there is the Pt of excellent properties2Bi1/ C catalyst.
Compared with prior art, the present invention provides the preparation method that a kind of simple carbon of step carries PtBi alloys, simplify
Reaction step has obtained the Pt with alloy phase2Bi1Nano-particle, Pt, Bi two-phase do not detach, and can be effectively formed alloy phase nanometer
Particle significantly improves electrocatalytic oxidation activity of the Pt sills to ethyl alcohol.
Description of the drawings
Fig. 1 is Pt in embodiment 12Bi1The STEM of/C catalyst schemes and its distribution diagram of element；
Fig. 2 is Pt in embodiment 12Bi1The XRD spectra of/C catalyst and commercial catalysts JM Pt/C；
Fig. 3 is Pt in embodiment 12Bi1/ C catalyst and commercial catalysts JM Pt/C are in 1mol L-1Sodium hydroxide and
1mol L-1Cyclic voltammetry figure in alcohol mixed solution.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment
A kind of Pt of high catalytic activity2Bi1The technical method of alloy nano elctro-catalyst, with steps are as follows：
(1) one-step synthesis method Pt2Bi1/ C nano catalyst
The rapid BiCl for weighing 8.08mg3And be dissolved in the ethylene glycol (EG) of 100mL, then weigh 21.28mg's
K2PtCl4Solid, the trisodium citrate of 115mg are dissolved in above-mentioned solution.1h is stirred, the Vulcan XC-72R for weighing 40mg live
Property carbon dust be added in above-mentioned solution, ultrasonic disperse 30min, and stir 2h.After the completion of waiting for the above process, by condensation reflux unit group
Install complete, the logical nitrogen 1h removing dissolved oxygens under liquid level, next, being warming up to 180 DEG C of condensing reflux 3h under nitrogen atmosphere.
(2) washing and drying of sample
After the liquid cooling in flask, filtering and washing is then washed with a large amount of ultra-pure waters (being more than 1L) and (is more than 3 for several times
It is secondary), finally 60 DEG C of dry 12h carry Pt to get to carbon in vacuum drying chamber2Bi1Alloy (Pt2Bi1/ C) nanometer electrical catalyst.
Fig. 1 is Pt2Bi1The STEM of/C catalyst schemes and its distribution diagram of element, it can be seen that Pt2Bi1The Pt of/C catalyst,
Bi Elemental redistributions the same area and shape it is similar and corresponding with the region of left figure metallic, illustrate two kinds of metals of Pt, Bi
Metal nanoparticle is collectively formed, there is a phenomenon where Pt, Bi split-phases to grow.
Fig. 2 is Pt2Bi1The XRD spectra of/C catalyst and commercial catalysts JM Pt/C, it is observed that the spy of corresponding Pt
Peak is levied, Pt is in face-centered cubic crystal form；The characteristic peak of PtBi alloy phases, PtBi exist with hexagonal structure, this illustrates in the present invention
Material forms PtBi alloys.
Fig. 3 is Pt2Bi1/ C nano catalyst and commercial catalysts JM Pt/C are in 1mol L-1Sodium hydroxide and 1mol L-1
Cyclic voltammetry figure in alcohol mixed solution, in test chart, it will be evident that Pt2Bi1The oxidation peak of/C nano catalyst
Current density has obtained significant enhancing, about the 1.9 of commercial catalysts JM Pt/C times, this illustrates that the introducing of Bi elements has
Imitate the ethanol electrooxidation activity of reinforcing material.
The present invention is a kind of synthesis carbon load alloy-type Pt simple to operation2Bi1The method of/C catalyst, the catalysis of preparation
Two kinds of Elemental redistributions of agent metal nanoparticle are uniform, and the characteristic peak with alloy phase can be confirmed that form alloy errorless, and use
In the catalytic oxidation process of ethyl alcohol, the chemical property significantly increased is shown.
Claims (8)
1. a kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity, which is characterized in that including following step
Suddenly：
(1) bismuth source is dissolved in reproducibility solvent, platinum source and stabilizer is then added, stirs and evenly mixs；
(2) activated carbon powder is added in the mixed solution of step (1), is uniformly dispersed；
(3) mixed solution of step (2) is passed through nitrogen deoxygenation, heats later and carries out condensing reflux；
(4) after the cooling of step (3) mixed solution, filtering and washing is carried out, is finally dried to get to product.
2. a kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity according to claim 1,
It is characterized in that, the bismuth source described in step (1) is BiCl3, the platinum source is K2PtCl4, wherein bismuth element rubs with platinum element
You are than being 1：2.
3. a kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity according to claim 1,
It is characterized in that, the reproducibility solvent described in step (1) is ethylene glycol.
4. a kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity according to claim 1,
It is characterized in that, the stabilizer described in step (1) is trisodium citrate.
5. a kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity according to claim 1,
It is characterized in that, the activated carbon powder described in step (2) is Vulcan XC-72R activated carbon powders.
6. a kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity according to claim 1,
It is characterized in that, step (2) carries out ultrasonic disperse after activated carbon powder is added.
7. a kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity according to claim 1,
It is characterized in that, step (3) is heated to 180 DEG C of condensing reflux 3h under nitrogen atmosphere.
8. a kind of preparation method of the platinum bismuth alloy fuel battery anode catalyst of high activity according to claim 1,
It is characterized in that, step (4) uses milli-Q water for several times, in 60 DEG C of dry 12h in vacuum drying chamber.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755593A (en) * | 2018-12-10 | 2019-05-14 | 上海电力学院 | A kind of PdBi alloy fuel cell anode catalyst of high activity and preparation method thereof |
| CN111446459A (en) * | 2020-04-24 | 2020-07-24 | 贵州大学 | High-performance anode electrocatalyst for methanol fuel cell and synthesis method |
Citations (3)
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| CN101279255A (en) * | 2008-04-17 | 2008-10-08 | 中国科学院上海微***与信息技术研究所 | Method for directly preparing nano-catalyst based on Pd for alcohol fuel battery |
| US20130084502A1 (en) * | 2011-09-30 | 2013-04-04 | Uchicago Argonne | Intermetallic Nanoparticles |
| CN103887529A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | M1 + M2/C catalyst and its preparation method |
-
2018
- 2018-04-18 CN CN201810349293.2A patent/CN108598496A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279255A (en) * | 2008-04-17 | 2008-10-08 | 中国科学院上海微***与信息技术研究所 | Method for directly preparing nano-catalyst based on Pd for alcohol fuel battery |
| US20130084502A1 (en) * | 2011-09-30 | 2013-04-04 | Uchicago Argonne | Intermetallic Nanoparticles |
| CN103887529A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | M1 + M2/C catalyst and its preparation method |
Non-Patent Citations (3)
| Title |
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| C. JEYABHARATHI等: "Methanol tolerant oxygen-reduction activity of carbon supported platinum–bismuth bimetallic nanoparticles", 《J APPL ELECTROCHEM》 * |
| KUN JIANG等: "Carbon supported Pd-Pt-Cu nanocatalysts for formic acid electrooxidation: Synthetic screening and componential functions", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| M. YOVANOVICH等: "PtBi/C Electrocatalysts for Formic Acid Electro-Oxidation in Acid and Alkaline Electrolyte", 《INT.J.ELECTROCHEM.SCI.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755593A (en) * | 2018-12-10 | 2019-05-14 | 上海电力学院 | A kind of PdBi alloy fuel cell anode catalyst of high activity and preparation method thereof |
| CN111446459A (en) * | 2020-04-24 | 2020-07-24 | 贵州大学 | High-performance anode electrocatalyst for methanol fuel cell and synthesis method |
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Application publication date: 20180928 |