CN103877972B - MnO in a kind of raising electrodexthe method of catalytic oxygen reduction activity - Google Patents
MnO in a kind of raising electrodexthe method of catalytic oxygen reduction activity Download PDFInfo
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- CN103877972B CN103877972B CN201210563966.7A CN201210563966A CN103877972B CN 103877972 B CN103877972 B CN 103877972B CN 201210563966 A CN201210563966 A CN 201210563966A CN 103877972 B CN103877972 B CN 103877972B
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Abstract
The advantages such as MnOx catalyst has preferable oxygen reduction activity in the basic conditions, and it has with low cost simultaneously, and preparation is simple.But Mn is mixed valence in the generally MnOx of preparation, and the relatively low Mn of valence state is poor to oxygen reduction reaction activity.The present invention is a kind of method improving MnOx catalytic oxygen reduction activity, it is specially and by cyclic voltammetry scan or linear scanning or constant potential, MnOx catalyst is carried out electrochemical treatments in the basic conditions, increase high-valence state Mn (IV) content in MnOx catalyst, thus improve the oxygen reduction activity of catalyst.The method has the advantages such as simple, reliable and stable.
Description
Technical field
The present invention relates to fuel-cell catalyst field, more particularly to a kind of method improving MnOx catalytic oxygen reduction activity under the conditions of alkalescence.
Background technology
Along with the consumption of the fuel such as coal, oil and natural gas is the most exhausted with the reserves of day sharp increase and energy resources, the energy technology finding environmental friendliness sustainable development is extremely urgent.Fuel cell has the advantages such as high, pollution-free, the noiselessness of energy conversion efficiency because of it, it has also become the focus of countries in the world research.
Fuel cell technology includes Proton Exchange Membrane Fuel Cells, SOFC, metal air fuel cell and alkaline anion-exchange membrane fuel cell etc..On the current technology, its cost is high and is limited by noble metal catalyst resource for Proton Exchange Membrane Fuel Cells；SOFC needs to carry out under the high temperature conditions；Metal-air battery fuel is in plentiful supply, length storage life, noise are low, oxygen electrode can use non noble metal oxygen reduction catalyst；And alkaline anion-exchange membrane fuel cell, compared with Proton Exchange Membrane Fuel Cells, there is not the problem causing electrode potential to decline because of fuel infiltration, may be used without non-Pt oxygen reduction catalyst simultaneously.
Mn oxide MnOx has good oxygen reduction catalytic activity, and cheap, aboundresources, has broad application prospects.At present, MnOx is the conventional ORR catalyst of metal-air battery and alkalescence (anion exchange membrane) fuel cell.Have the different valence states such as Mn (II), Mn (III), Mn (IV) due to Mn, therefore its oxide there is also various ways: MnO2、Mn2O3、Mn3O4、Mn5O8And MnOOH etc..Research is thought, the Mn of high-valence state is higher to the activity of ORR.Additionally, in electrochemical environment, along with the valence state of the change catalyst surface Mn of current potential also can change therewith, the change causing surface MnOx to form, cause ORR activity to change.
Summary of the invention
For the deficiencies in the prior art, present invention aim at providing a kind of method improving MnOx catalytic oxygen reduction activity, the method passes through electrochemical treatments MnOx catalyst so that MnOx catalyst surface Mn (IV) content increases, thus improves the oxygen reduction activity of MnOx catalyst.
For achieving the above object, the present invention uses scheme in detail below to realize:
A kind of improve the method for MnOx catalytic oxygen reduction activity in electrode, under the conditions of alkalescence, use cyclic voltammetry scan or linear scanning or potentiostatic scanning, MnOx catalyst in electrode is carried out electrochemical treatments, increases Mn (IV) content in MnOx catalyst and improve the oxygen reduction activity of catalyst.
In electrode, MnOx is Mn3O4, any one or Mn in MnO3O4Mixture or Mn with MnO3O4With MnO2Mixture, Mn3O4With MnO2Mixture in MnO2Mass content 0.01-99.9%.
In the alkaline electrolyte, with be supported with MnOx catalyst electrode as working electrode, with Hg/HgO as reference electrode, MnOx catalyst is processed by cyclic voltammetry scan or linear scanning or constant potential Electrochemical Scanning, part Mn (II) making MnOx catalyst surface is converted into Mn (IV), then improves the oxygen reduction activity of MnOx catalyst.
The current potential of described cyclic voltammetry scan or linear scanning or potentiostatic scanning electrochemical treatments is 0-0.3V relative to Hg/HgO reference electrode.
The described electrochemical treatments time is 0.05-1h.
Described alkaline electrolyte is akaline liquid electrolyte or alkali solid electrolyte.
Described akaline liquid electrolyte or be NaOH aqueous solution, or be KOH aqueous solution, or be the mixed aqueous solution of NaOH and KOH, and the hydroxide ion concentration in akaline liquid electrolyte is 0.1-5M；
Described alkali solid electrolyte is quaternary anion exchange membrane or alkali metal hydroxide doping type anion exchange membrane.
MnOx catalyst loading in electrode is 0.1-50mg cm-2。
Described MnOx catalyst can use hydrothermal synthesis method to prepare, it would however also be possible to employ prepared by additive method.
The preparation process of described MnOx catalyst slurry includes: 1. weigh a certain amount of MnOx catalyst (wherein containing MnO in MnOx catalyst2、Mn2O3、Mn3O4、Mn5O8And in MnOOH one or more), 2. ethanol and Nafion resin it are sequentially added into, ethanol is 50:1-10:1 with the mass ratio of MnOx, Nafion Yu MnOx mass ratio is 1:20-1:1,3. MnOx catalyst slurry is obtained after being uniformly dispersed, 4. step 3. gained catalyst slurry is evenly applied to Pt sheet or other conductive substrates surface, prepares working electrode.
The present invention compared with prior art has such advantages as and effect:
(1) use electrochemical process for treating of the present invention to add the Mn content of the high-valence state in MnOx, reduce the Mn content of lower valency, thus reduce the lower valency Mn impact for hydrogen reduction process, improve the oxygen reduction activity of MnOx catalyst.
(2) advantages such as the method has simply, operation controllability is strong.
Accompanying drawing explanation
Fig. 1 is MnOxCatalyst is the XPS spectrum figure of Mn2p before and after cyclic voltammetry scan.As seen from Figure 1, the spin-spin splitting of Mn2p track is Mn2p1/2And Mn2p3/2, in conjunction with laying respectively near 642.0 and 653.5eV, it is spaced 11.5 ± 0.1eV.Spectral peak is carried out swarming matching, three kinds of MnOxAll comprising four to dual division peak in catalyst, can be respectively belonging to Mn (II), Mn (III) by species from low to high by combining, the shake of Mn (IV) and Mn2p swashs peak.For undressed MnOxCatalyst, the Mn (II) on its surface, Mn (III) and Mn (IV) content are respectively 15%, 49% and 36%；After 0-0.3V scan round, Mn (IV) content of catalyst surface adds 14%；And after-0.8 ~-0.4V scans, catalyst surface Mn (III) content is almost unchanged, and the Mn (IV) that there are about 20% is converted into Mn (II).
Fig. 2 is MnO after different potentials interval is scannedxThe ORR polarization curve of catalyst.Sweep speed is 10mVs-1, electrode rotating speed is 1600rpn.After 0-0.3V scans, the half wave potential of ORR polarization curve is shuffled about 30mV, MnOxThe catalysis activity of ORR is significantly improved.By contrast, after-0.8～-0.4V scans, the negative up to 80mV that moves of half wave potential, the initial reduction current potential also negative activity moving about 100mV, MnOx catalyst substantially reduces simultaneously.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is explained in detail.Certainly the present invention is not limited in these specific embodiments.
Comparative example:
Weigh the MnO that 30mg preparesxCatalyst, is sequentially added into 2mL ethanol and Nafion emulsion that 67mg mass fraction is 5%, by ultrasonic disperse uniformly after serosity be coated on Pt electrode surface and obtain working electrode.With Pt sheet for electrode, Hg/HgO electrode is reference electrode, with 10mVs between-0.8 ~-0.4V-1Speed of sweeping be circulated voltammetric scan (20 circle), electrode rotating speed is the negative up to 80mV that moves of half wave potential of 1600rpn, ORR polarization curve, and the initial reduction current potential also negative activity moving about 100mV, MnOx catalyst substantially reduces, as shown in Figure 2 simultaneously.
Embodiment 1:
Weigh the MnO that 30mg preparesxCatalyst, is sequentially added into 2mL ethanol and Nafion emulsion that 67mg mass fraction is 5%, by ultrasonic disperse uniformly after serosity be coated on Pt electrode surface and obtain working electrode.With Pt sheet for electrode, Hg/HgO electrode is reference electrode, with 10mVs between 0-0.3V-1Speed of sweeping be circulated voltammetric scan (20 circle), electrode rotating speed is that the half wave potential of 1600rpn, ORR polarization curve is shuffled about 30mV, MnOxThe catalysis activity of ORR is significantly improved, as shown in Figure 2.
Embodiment 2:
Weigh the MnO that 30mg preparesxCatalyst, is sequentially added into 2mL ethanol and Nafion emulsion that 67mg mass fraction is 5%, by ultrasonic disperse uniformly after serosity be coated on Pt electrode surface and obtain working electrode.With Pt sheet for electrode, Hg/HgO electrode is reference electrode, and after maintaining 5min under the current potential of 0.2V, its ORR catalysis activity is improved significantly.
Embodiment 3:
Weigh the MnO that 30mg preparesxCatalyst, is sequentially added into 2mL ethanol and Nafion emulsion that 67mg mass fraction is 5%, by ultrasonic disperse uniformly after serosity be coated on Pt electrode surface and obtain working electrode.With Pt sheet for electrode, Hg/HgO electrode is reference electrode, with 1mVs-1Speed of sweeping in 0.0-0.4V potential window, carry out linear scanning, its ORR catalysis activity is improved significantly.
Claims (7)
1. one kind is improved the method for MnOx catalytic oxygen reduction activity in electrode, it is characterised in that: under the conditions of alkalescence,
Use cyclic voltammetry scan or linear scanning or potentiostatic scanning, the MnOx catalyst in electrode is carried out at electrochemistry
Reason, increases Mn (IV) content in MnOx catalyst and improves the oxygen reduction activity of catalyst；
In electrode, MnOx is Mn3O4, any one or Mn in MnO3O4Mixture or Mn with MnO3O4
With MnO2Mixture, Mn3O4With MnO2Mixture in MnO2Mass content 0.01-99.9%.
2. the method for claim 1, it is characterised in that:
In the alkaline electrolyte, be supported with MnOx catalyst electrode as working electrode, with Hg/HgO for reference electricity
Pole, by cyclic voltammetry scan or linear scanning or potentiostatic scanning electrochemical treatments MnOx catalyst, makes MnOx urge
Part Mn (II) on agent surface is converted into Mn (IV), then improves the oxygen reduction activity of MnOx catalyst.
3. method as claimed in claim 2, it is characterised in that: described cyclic voltammetry scan or linear scanning or permanent electricity
The current potential of bit scan electrochemical treatments is 0-0.3V relative to Hg/HgO reference electrode.
4. method as claimed in claim 1 or 2, it is characterised in that: the described electrochemical treatments time is 0.05-1h.
5. method as claimed in claim 2, it is characterised in that: described alkaline electrolyte be akaline liquid electrolyte or
Alkali solid electrolyte.
6. method as claimed in claim 5, it is characterised in that: described akaline liquid electrolyte or be that NaOH is water-soluble
Liquid, or be KOH aqueous solution, or be the mixed aqueous solution of NaOH and KOH, and the hydrogen-oxygen in akaline liquid electrolyte
Ion concentration is 0.1-5M；
Described alkali solid electrolyte is quaternary anion exchange membrane or the friendship of alkali metal hydroxide doping type anion
Change film.
7. the method for claim 1, it is characterised in that:
MnOx catalyst loading in electrode is 0.1-50mg cm-2。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1312411A2 (en) * | 2001-11-20 | 2003-05-21 | Rohm And Haas Company | Electroactive catalysis |
| CN101011666A (en) * | 2006-01-31 | 2007-08-08 | 罗门哈斯公司 | Regenerated mixed metal oxide catalysts |
| CN101370585A (en) * | 2006-01-12 | 2009-02-18 | 乔治洛德方法研究和开发液化空气有限公司 | Process for the preparation of a catalytic specie using electro-deposition |
| CN101623637A (en) * | 2009-07-23 | 2010-01-13 | 天津大学 | Catalyst Au/MnOx-CeO2 used for preferential oxidation of carbon monoxide and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1312411A2 (en) * | 2001-11-20 | 2003-05-21 | Rohm And Haas Company | Electroactive catalysis |
| CN101370585A (en) * | 2006-01-12 | 2009-02-18 | 乔治洛德方法研究和开发液化空气有限公司 | Process for the preparation of a catalytic specie using electro-deposition |
| CN101011666A (en) * | 2006-01-31 | 2007-08-08 | 罗门哈斯公司 | Regenerated mixed metal oxide catalysts |
| CN101623637A (en) * | 2009-07-23 | 2010-01-13 | 天津大学 | Catalyst Au/MnOx-CeO2 used for preferential oxidation of carbon monoxide and preparation method thereof |
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