CN1787961A - Method for manufacturing nanostructured manganese oxide having dendritic structure, and oxygen reduction electrode comprising nanostructured transition metal oxide having dendritic structure - Google Patents
Method for manufacturing nanostructured manganese oxide having dendritic structure, and oxygen reduction electrode comprising nanostructured transition metal oxide having dendritic structure Download PDFInfo
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- CN1787961A CN1787961A CNA2005800003808A CN200580000380A CN1787961A CN 1787961 A CN1787961 A CN 1787961A CN A2005800003808 A CNA2005800003808 A CN A2005800003808A CN 200580000380 A CN200580000380 A CN 200580000380A CN 1787961 A CN1787961 A CN 1787961A
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Abstract
An oxygen reduction electrode having excellent oxygen reduction characteristics (oxygen reduction catalyst performance). Provided are: (1) a process for producing a nanostructured manganese oxide having a dendritic structure made up of aggregated primary particles, which comprises the steps of preparing a gas atmosphere which is a mixed gas comprising an inert gas and oxygen and has an oxygen proportion of 0.05 to 0.5% in terms of flow rate ratio by mass, irradiating a target plate comprising a manganese oxide with a laser light in the gas atmosphere to thereby cause the target plate to release constituent substances thereof, and depositing the released substances on a substrate disposed so as to face the target plate almost in parallel to thereby obtain the nanostructured manganese oxide having a dendritic structure; and (2) an oxygen reduction electrode containing a nanostructured transition metal oxide having a dendritic structure made up of aggregated primary particles.
Description
Technical field
The oxygen reduction electrode that the present invention relates to have the manganese oxide structure method of dendritic crystal body structure and contain transition metal oxide nano structure with dendritic crystal body structure.
Background technology
The material that had fine structure in the past obtains by composites such as metal, alloy, compound are solidified rapidly, nearly all is the material with a few micron dimension particle sizes.In addition, in recent years, make scantling quite active from the little research of micron to nano material.Is that to be present in the atom ratio of particle boundary (surface) quite high with this nano particle as the feature of the nanostructure at center, for example can reach 40% in the nano particle of 5nm.When nanostructure compared with the micro materials with identical chemical composition, chemistry and physical characteristic had very big-difference, show the characteristic of a lot of excellences.
For example, Mn oxide (MnO
x) be difficult to obtain as nanostructure now.Usually, the synthetic transition metal oxide particle of commercially available usefulness is of a size of micron dimension.And the Mn oxide of micron dimension also has report as the characteristic of oxygen reduction catalyst.For example, according to patent documentation 1, the Mn oxide material of different oxidation state (valence mumber) has different catalytic activitys, the Mn of the manganese compound of trivalent
2O
3Be higher than the different Mn of valence mumber with the hydrogen reduction catalytic activity of MnOOH
3O
4And Mn
5O
8, respectively near-0.3V and-observe the hydrogen reduction current potential near the 1.0V.
On the other hand, as the preparation method of nanostructure, with manganese dioxide (MnO
2) be example, known have potassium permanganate (KMnO
4) aqueous solution is sprayed onto and dissolved manganese sulfate (MnSO
4) aqueous sulfuric acid in, produce synthetic reaction, after separating out, methods of heating treatment (1, the 42 page of patent documentation, the 2nd figure).
Moreover, be example with the oxygen reduction electrode of using Mn oxide, the known example (patent documentation 2, the 8th page, Fig. 2) that the mixture of the pulverous mangano-manganic oxide that uses micron dimension and manganese dioxide is arranged as the air zinc battery of oxygen reduction electrode.
As the document relevant, can list patent documentation 3,4, non-patent literature 1,2 etc. in addition with the present invention.
Patent documentation 1: special table 2000-505040 communique
Patent documentation 2: the spy opens flat 10-302808 communique
Patent documentation 3: the spy opens 2000-144387 communique (especially [0015] paragraph)
Patent documentation 4: the spy opens the 2003-306319 communique
Non-patent literature 1:Journal of The Electrochemical Society, 149 (4) A504-A507 (2002)
Non-patent literature 2: laser research Volume 28, Number in June, 6,2000 348-353 page or leaf
Summary of the invention
High surface area material with nanostructured, the chemical reaction of mediating at active site realize aspect the purposes (purposes of catalysis) of important function useful especially.This material is the bigger the better with the contact area of surrounding environment (gas, liquid etc.) in catalytic reaction.For this reason, catalyst material is formed nanostructure, have extremely significantly advantage.
And then when transition metal oxide was used as the catalyst material of oxygen reduction electrode, the oxygen reduction electrode current potential was the smaller the better, considered that from the viewpoint of cost loading amount is few more good more.
The present invention carries out in view of above-mentioned viewpoint, and main purpose provides the oxygen reduction electrode with excellent hydrogen reduction characteristic (hydrogen reduction catalytic capability).
The inventor through further investigation, found that the material by having specific fine structure is used as oxygen reduction electrode for achieving the above object, and can achieve the above object, and so far finish the present invention.
That is the oxygen reduction electrode that the present invention relates to have the manganese oxide structure manufacture method of following dendritic crystal body structure and contain transition metal oxide nano structure, with dendritic crystal body structure.
1. the manufacture method of a manganese oxide structure, this manganese oxide structure has by the coalescent dendritic crystal body structure that forms of primary particle, wherein, with the mist of inert gas and oxygen as atmosphere gas, oxygen ratio in the above-mentioned atmosphere gas is counted more than 0.05% below 0.5% with mass flow ratio, in above-mentioned atmosphere gas, by laser being radiated on the target plate that forms by Mn oxide, the constitute of target plate is broken away from, and make this disengaging material be deposited in above-mentioned target plate almost parallel opposing substrates on, obtain above-mentioned manganese oxide structure with dendritic crystal body structure.
2. as above-mentioned 1 described manufacture method, it is characterized in that, using with above-mentioned manganese oxide structure as working electrode, with platinum as to electrode, with silver/silver chlorate as reference electrode, and in the cyclic voltammogram that obtains as the cyclic voltammetry of three utmost point electrolytic cells of electrolyte with the potassium hydroxide aqueous solution of concentration 0.1mol/L and pH value 13, near-0.2V, show the hydrogen reduction current potential.
3. as above-mentioned 1 described manufacture method, it is characterized in that above-mentioned inert gas is a helium.
4. as above-mentioned 1 described manufacture method, it is characterized in that, by providing energy to make its activation to above-mentioned atmosphere gas.
5. as above-mentioned 1 described manufacture method, it is characterized in that above-mentioned atmosphere gas has the following pressure of the above 1333Pa of 13.33Pa.
6. as above-mentioned 1 described manufacture method, it is characterized in that above-mentioned laser is the pulse laser with the following pulse width of the above 20ns of 5ns.
7. as above-mentioned 1 described manufacture method, it is characterized in that above-mentioned laser has 0.5J/cm
2Above 2J/cm
2Following energy density.
8. as above-mentioned 1 described manufacture method, it is characterized in that above-mentioned target plate is the sintered body of Mn oxide.
9. as above-mentioned 1 described manufacture method, it is characterized in that having the operation of the further heating of manganese oxide structure that will obtain.
10. as above-mentioned 1 described manufacture method, it is characterized in that, the pressure of above-mentioned atmosphere gas is changed.
11. as above-mentioned 1 described manufacture method, it is characterized in that having: before above-mentioned operation, in advance target plate and substrate are oppositely arranged in parallel to each other the operation in the reaction system.
12. as above-mentioned 1 described manufacture method, it is characterized in that, have in order to control the size that is formed near the HTHP zone the above-mentioned target plate on the above-mentioned target plate, to 1 by laser is radiated at) pressure and 2 of atmosphere gas) at least one operation of adjusting of distance of above-mentioned target plate and substrate.
13. an oxygen reduction electrode is characterized in that, contains: have transition metal oxide nano structure by the coalescent dendritic crystal body structure that forms of primary particle.
14., it is characterized in that above-mentioned transition metal is a manganese as above-mentioned 13 described oxygen reduction electrodes.
15., it is characterized in that above-mentioned primary particle has the following average grain diameter of the above 20nm of 2nm as above-mentioned 13 described oxygen reduction electrodes.
16., it is characterized in that above-mentioned dendritic crystal body structure has the following average height of the above 20 μ m of 1 μ m as above-mentioned 13 described oxygen reduction electrodes.
17., it is characterized in that above-mentioned primary particle has the following average grain diameter of the above 20nm of 2nm as above-mentioned 13 described oxygen reduction electrodes, and above-mentioned dendritic crystal body structure has the following average height of the above 20 μ m of 1 μ m.
18. as above-mentioned 13 described oxygen reduction electrodes, it is characterized in that, using with above-mentioned manganese oxide structure as working electrode, with platinum as to electrode, with silver/silver chlorate as reference electrode, and in the cyclic voltammogram that obtains as the cyclic voltammetry of three utmost point electrolytic cells of electrolyte with the potassium hydroxide aqueous solution of concentration 0.1mol/L and pH value 13, near-0.2V, show the hydrogen reduction current potential.
19., it is characterized in that above-mentioned transition metal is a manganese as above-mentioned 18 described oxygen reduction electrodes.
20. as above-mentioned 13 described oxygen reduction electrodes, it is characterized in that above-mentioned transition metal oxide nano structure is at least a transition metal oxide that is selected from an oxidation transition metal, four oxidations, three transition metal, three oxidations, two transition metal and the titanium dioxide transition metal.
21., it is characterized in that above-mentioned transition metal oxide nano structure is at least a Mn oxide that is selected from manganese monoxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and the manganese dioxide as above-mentioned 13 described oxygen reduction electrodes.
22., it is characterized in that above-mentioned transition metal oxide nano structure is formed on the conductive base material as above-mentioned 13 described oxygen reduction electrodes.
23. as above-mentioned 18 described oxygen reduction electrodes, it is characterized in that above-mentioned cyclic voltammogram shows the hydrogen reduction current potential in-scope below the above 0V of 0.25V.
24., it is characterized in that above-mentioned transition metal is a manganese as above-mentioned 23 described oxygen reduction electrodes.
Manufacture method of the present invention, because by carrying out laser ablation with so-called coaxial (on-axis), make the transition metal oxide nano structure, so can make (forming) by the coalescent transition metal oxide nano structure that forms of primary particle with dendritic crystal body structure by the minimum component unit of the particle shape with high crystalline.
In addition, manufacturing method according to the invention, irradiation by laser (mainly is an atom by the material that target material penetrates, ion, Particle Cluster) with atmosphere gas interact (collision, scattering, restriction effect) reach optimization, the valence mumber of the transition metal that can control in the transition metal oxide thus to be contained and the fine structure of nano-scale.
Oxygen reduction electrode of the present invention, by containing (forming) by the coalescent transition metal oxide nano structure that forms of primary particle with dendritic crystal body structure by the minimum component unit of the particle shape with high crystalline, owing to have sizable specific area, present excellent catalytic activity, so can give play to excellent hydrogen reduction catalytic capability.
Description of drawings
Fig. 1 is in embodiment of the present invention 1, contains the electron scanning micrograph by the manganese oxide structure of the coalescent dendritic crystal body structure that forms of the primary particle with high crystalline.
Fig. 2 is in embodiment of the present invention 1, contains the TEM photo by the manganese oxide structure of the coalescent dendritic crystal body structure that forms of the primary particle with high crystalline.
Fig. 3 is illustrated in the embodiment of the present invention, the pie graph of employed nanostructure manufacturing installation in the preparation method of manganese oxide structure.
Fig. 4 is in embodiment of the present invention 2, contains the electron scanning micrograph by the manganese oxide structure of the coalescent dendritic crystal body structure that forms of the primary particle with high crystalline.
Fig. 5 is in embodiment of the present invention 2, contains the TEM photo by the manganese oxide structure of the coalescent dendritic crystal body structure that forms of the primary particle with high crystalline.
Fig. 6 is in embodiment of the present invention 3, contains the electron scanning micrograph by the manganese oxide structure of the coalescent dendritic crystal body structure that forms of the primary particle with high crystalline.
Fig. 7 is in embodiment of the present invention 3, contains the TEM photo by the manganese oxide structure of the coalescent dendritic crystal body structure that forms of the primary particle with high crystalline.
Fig. 8 is in comparative example 1 of the present invention, has the electron scanning micrograph of the manganese oxide structure of column structure.
Fig. 9 (a) is the figure of expression " coaxial (on-axis) state ", (b) is the figure of expression " from axle (off-axis) state ".
Figure 10 is in comparative example 2 of the present invention, has the electron scanning micrograph of the manganese oxide structure of cotton candy structure.
Figure 11 is mask pattern figure used among the embodiment 1.
Figure 12 is electrode mode figure used among the embodiment 1.
Figure 13 is the current density curve map of measuring among the embodiment 1.
Symbol description
301 reative cells, 302 ultrahigh vacuum gas extraction system
303a, 303b mass flow controller
304 gas introduction tube lines, 305 gases are discharged system
306 target supports, 307 targets
308 pulsed laser sources 309 are piled up substrate
310 laser import window 311 slits
312 lens, 313 speculums
314 columns of smoke (Plume)
The specific embodiment
1. oxygen reduction electrode
Oxygen reduction electrode of the present invention, feature are to contain: have the transition metal oxide nano structure by the coalescent dendritic crystal body structure that forms of primary particle.So-called " skeleton " is defined as branch and regulation crystallographic direction the be in line crystalline growth structure of shape of branch abreast, be the structure the same, but " dendritic crystal body structure " meaning is that " outward appearance " is the agglomerate of dendritic crystal shape (being dendroid) in the specification of the present invention with so-called dendritic crystal.Therefore, " structure of skeleton " is different with the crystalline growth of skeleton.
Oxygen reduction electrode of the present invention as electrode material (special electrode active material (catalyst material)), uses the transition metal oxide nano structure that has by the coalescent dendritic crystal body structure that forms of primary particle at least.Above-mentioned primary particle is emboliform minimum component unit, especially preferably can obviously confirm the high crystalline particle of lattice.By making transition metal oxide form nanostructure, can on small primary particle, have considerable catalyst activity point, can realize the unexistent excellent hydrogen reduction catalytic capability of general bulk material.
Electrode of the present invention as electrode material, except using above-mentioned transition metal oxide nano structure, also can use known oxygen reduction electrode inscape.For example, under the state that forms above-mentioned transition metal oxide nano structure on the conductive base material, use.
The average grain diameter of above-mentioned primary particle is unqualified, in the preferred usually scope below the above 20nm of 2nm, more preferably in the scope below the above 7nm of 3nm.
In addition, the average height of the coalescent dendritic crystal body structure (secondary structure) that forms of above-mentioned primary particle is also unqualified, and is usually preferred more than 1 μ m in the scope below the 20 μ m, more preferably more than 5 μ m in the scope below the 15 μ m.In addition, the height of the said dendritic crystal body structure meaning is the length of the branch of dendritic crystal.The branch of dendritic crystal body structure (dendroid post) diameter is also unqualified, and is usually preferred more than 0.5 μ m in the scope below the 5 μ m.The shape of dendritic crystal body structure is unqualified, for example, can form membranaceous use.
Oxygen reduction electrode of the present invention, using with this electrode as working electrode, with platinum as to electrode, with silver/silver chlorate as reference electrode, and in the cyclic voltammogram that obtains as the cyclic voltammetry of three utmost point electrolytic cells of electrolyte with the potassium hydroxide aqueous solution of concentration 0.1mol/L and pH value 13, near-0.2V (preferred-below the above 0V of 0.25V) demonstration hydrogen reduction current potential.That is, electrode of the present invention can have been given play to oxygen reducing ability under than existing lower voltage.
Above-mentioned cyclic voltammetry is more specifically said, can adopt the condition of following embodiment 1.Especially as test electrode, can use to form transition metal oxide nano structure (diameter 2mm, thickness 7 μ m) on the round central part on vitreous carbon 501 (diameter 3mm * height 3mm) and be fixed in structure on the copper rod.
Oxygen reduction electrode of the present invention, as electrode material, except using above-mentioned transition metal oxide nano structure, other inscapes of electrode, assemble method etc. do not have particular determination.That is, for example, use transition metal oxide nano structure and known other inscapes,, make oxygen reduction electrode of the present invention according to known assemble method by manufacture method manufacturing shown in following.
2. the manufacture method that has the transition metal oxide nano structure of dendritic crystal body structure.
Has manganese oxide structure coalescent by primary particle and the dendritic crystal body structure that forms, manufacture method by following characteristics is made, promptly, with the mist of inert gas and oxygen as atmosphere gas, oxygen ratio in the above-mentioned atmosphere gas is counted more than 0.05% below 0.5% with mass flow ratio, have: in above-mentioned atmosphere gas, laser is radiated on the target plate that is formed by Mn oxide, the constitute of target plate is broken away from, make the material of this disengaging be deposited in above-mentioned target plate almost parallel opposing substrates on, obtain having the operation of the manganese oxide structure of above-mentioned dendritic crystal body structure.
Also be described among embodiment and the embodiment, but in manufacture method of the present invention, the oxygen ratio in the atmosphere gas is with respect to inert gas (for example, as embodiment, be example in He gas) mass flow ratio be set at more than 0.05% below 0.5%.
Mass flow ratio is lower than at 0.05% o'clock, though can obtain being agglomerated into the nanostructure of column structure, different with desired nanostructure (nanostructure) with dendritic crystal body structure.In addition, mass flow ratio surpasses at 0.5% o'clock, though obtain being agglomerated into the nanostructure of cotton candy shape, these are also different with desired nanostructure.
In fact, target plate and substrate configured in parallel.This is called " coaxial (on-axis) " state.When being not configured in parallel, promptly, can not get desired nanostructure with dendritic crystal body structure with " from axle (off-axis) " state.
For obtaining nanostructure,,, can use various Mn oxides so long as it is just passable, unqualified to become the target material of laser as the Mn oxide of initiation material.For example can use manganese monoxide (MnO), mangano-manganic oxide (Mn
3O
4), manganese sesquioxide managnic oxide (Mn
2O
3) and manganese dioxide (MnO
2) at least a.In this case, preferably identical oxide with needed manganese oxide structure.For example, when wanting to make the nanostructure of mangano-manganic oxide, the preferred target plate that uses the sintered body by mangano-manganic oxide to form.
Mn oxide can be crystal or non-crystal any.During crystal, can use many crystallizations or mcl any.Therefore, for example can use the sintered body etc. of Mn oxide.
The target plate shape that forms by Mn oxide, so long as the shape of suitable laser irradiation just can, unqualified.For example, the Mn oxide about below the above 10mm of thickness 0.5mm can be used as target plate.Target plate also can be on suitable supporter stacked Mn oxide.The big I of target plate is according to the suitably settings such as condition of laser ablation method.
Substrate is not particularly limited, for example, can uses by Si, SiO
2Substrate etc. various materials formation.
Among the present invention, by to above-mentioned target plate illuminating laser beam, the constitute of target plate is broken away from, and make this disengaging material be deposited in above-mentioned target plate almost parallel opposing substrates on.That is, use laser ablation method (preferred pulse laser ablation method) among the present invention.Laser ablation method can utilize enforcements such as existing reaction unit.
So-called laser ablation method is to shine high-energy-density (particularly at 0.5J/cm on target
2More than, preferred 0.5J/cm
2Above 2J/cm
2Below) laser, with the method for target melt surface, disengaging.The pulse laser ablation method is to use the method for pulse laser as laser.
The feature of laser ablation method is a kind of thermal nonequilibrium and no qualitative process.As the concrete effect of thermal nonequilibrium enumerated can be spatially, excite selectively on the time.With regard to spatially selectively with regard to the excitability, benefit especially.That is, in the former heat treatment process or plasma process, the quite wide zone or the entire reaction groove of reactive tank all can be exposed in heat, the ion etc., opposite with it, in the laser ablation method, owing to only excite necessary substance source, so be to suppress the purification process that impurity is sneaked into.
So-called no qualitative, the meaning is and identical thermal nonequilibrium ion process comparison, has low especially damaging.In the laser ablation, the material of disengaging mainly is an ion and as atom, molecule, the Particle Cluster (by the atomic building about several to dozens of) of neutral particle, and its kinetic energy ion is that tens eV, neutral particle are a few eV levels.This is the energy that is higher than the heating evaporation atom far away, but is the energy area well below ion beam.
The minimum laser ablation process of damage in above-mentioned purification, suitable for making can control that impurity is sneaked into, the nanostructure of composition, crystallinity etc.This situation is made nanostructure in order to use laser ablation method, and target material preferably can absorb the Wavelength of Laser scope as light source.
In the manufacture method of the present invention, as laser, the pulse width when using pulse laser is preferably below the above 20ns of 5ns especially.Below the above 700nm of the general preferred 150nm of wavelength.Below the usually preferred above 500mJ of 10mJ of pulse energy.In addition, repetition rate is preferably below the above 1KHz of 5Hz usually.
The laser medium of laser (kind of laser) has no particular limits, and for example can adopt the Solid State Laser of the gas laser of excimer laser etc. or YAG laser etc.Excimer laser (especially using halogen gas and the rare gas excimer laser as laser medium) is used in special hope.For example, can suitably use with fluorine gas and argon gas ArF excimer laser as laser medium.
Especially, in the present invention, when piling up from material that above-mentioned target plate breaks away from, be with above-mentioned substance be deposited in target plate almost parallel opposing substrates on (Fig. 3).In other words, under the state of target plate and the mutual almost parallel of substrate, on substrate, pile up the disengaging material.This mode is to adopt the mode of so-called coaxial (on-axis) state, with the so-called mode difference from axle (off-axis) (under the state of target plate and the mutual arranged perpendicular of substrate, to the method for substrate accumulation) state of employing.Among the present invention, by pile up above-mentioned substance under coaxial (on-axis) state, the manganese oxide nanostructure that finally obtains is brought into play more excellent hydrogen reduction characteristic than adopting when axle (off-axis) state.
Therefore, when using existing reaction unit to implement laser ablation method under coaxial (on-axis) state, preferably in advance with above-mentioned target plate and substrate to be oppositely arranged in the reaction system in parallel to each other.
In addition, when using reaction unit, in order to control the size that is formed near the HTHP zone the above-mentioned target plate on the above-mentioned target plate, to 1 by laser is radiated at) pressure and 2 of atmosphere gas) at least one is adjusted in the distance of above-mentioned target plate and substrate.Thus, can on substrate, form manganese oxide structure effectively.
Manufacture method of the present invention as atmosphere gas, can be used the mist of inert gas and reactant gas (oxygen).According to the method, when only using inert gas, can ignore influence in remaining reactant gas kind such as chamber.
As inert gas, for example can use Ar, He, N
2Deng.Wherein preferred He gas.
The ratio of oxygen can be set in more than 0.05% below 0.5% in mass flow ratio in the atmosphere gas (above-mentioned mist), is preferably the scope below 0.3% more than 0.1%.
The pressure of atmosphere gas can be according to the suitably settings such as composition of atmosphere gas.From making the manganese oxide structure with the target material same composition well, preferably adjust in the following scope of the above 1333Pa of 13.33Pa.
Among the present invention, the pressure of atmosphere gas is changed.The structure (dendritic crystal body structure) of nanostructure on stacked direction can be controlled thus, and the rerum natura of manganese oxide structure can be controlled.
In addition, by providing energy, also can make the atmosphere gas activation to atmosphere gas.In view of the above, the valence mumber of manganese be can increase,, for example, UV-irradiation, electron beam irradiation etc. enumerated as the method that energy is provided to atmosphere gas.
Like this, by being deposited in from the material that target plate breaks away from the substrate, finally on substrate, form the manganese oxide structure that has by the coalescent dendritic crystal body structure that forms of primary particle.Generally be to utilize laser ablation method, the material (atom, molecule, ion, Particle Cluster etc.) that breaks away from from target plate is coalescent on one side or grow up be deposited on the substrate the final manganese oxide structure that has by the coalescent secondary structure that forms of primary particle (dendritic crystal body structure) that forms on one side on substrate.
Among the present invention, as required, also can further heat above-mentioned manganese oxide structure.By heating, can improve the oxidation number of Mn oxide.For example, manganese oxide structure is four manganese oxide (Mn
3O
4) time, by in oxidisability atmosphere gas, heating, obtain manganese sesquioxide managnic oxide (Mn
2O
3).Heating-up temperature does not have particular determination, is taken as usually more than 600 ℃, and higher limit can suitably be set.
With the manganese oxide structure that manufacture method of the present invention obtains, has the coalescent secondary structure that forms of primary particle (dendritic crystal body structure).Like this, on small primary particle, have considerable catalytic activity point, utilize the size of secondary structure can promote effective diffusion of reactive material.
The primary particle average grain diameter of formation secondary structure, the shape of secondary structure, size are like above-mentioned.
Below press embodiment, on one side with reference to accompanying drawing, the manufacture method to manganese oxide structure specifies on one side.
(embodiment 1)
In the embodiment 1, to by Mn oxide (MnO
x) nanostructure and the manufacture method thereof that form describe.
Fig. 1 is the electron scanning micrograph of manganese oxide structure in embodiment 1.Manganese oxide structure, as the top figure of Fig. 1 was clear and definite, primary particle was coalescent as can be known, formed the secondary structure of hundreds of nm.From the sectional view of Fig. 1 clear and definite, secondary structure has the dendritic crystal body structure of highly about 7.5 μ m as can be known.And then as TEM photo among Fig. 2 clear and definite, primary particle is a few nm particles that lattice can obviously be confirmed, crystallinity is very high as can be known.
Then, the manganese oxide structure preparation method with ingotism structure shown in Figure 1 is described.
In the embodiment 1, in atmosphere, use laser ablation, on substrate, pile up Mn oxide.So-called laser ablation method is to target material irradiation high-energy-density (pulse energy: 1.0J/cm
2About or more than it) laser, make the melt surface of illuminated target material, the method for disengaging.
The feature of laser ablation method is a kind of thermal nonequilibrium and no qualitative process.As the concrete effect of thermal nonequilibrium enumerated can be spatially, excite selectively on the time.With regard to spatially selectively with regard to the excitability, benefit especially.That is, in the former heat treatment process or plasma process, the quite wide zone or the entire reaction groove of reactive tank all are exposed in heat, the ion etc., opposite with it, in the laser ablation method, owing to only excite necessary substance source, so be to suppress the purification process that impurity is sneaked into.
So-called no qualitative, the meaning is to compare with identical thermal nonequilibrium ion process, has low especially damageability.In the laser ablation, the material that breaks away from mainly is an ion and as atom, molecule, the Particle Cluster (by the atomic building about several to dozens of) of neutral particle, the level that its kinetic energy can reach the level of tens eV when being ion, its kinetic energy can reach several eV when being neutral particle.This is the energy that is higher than the heating evaporation atom far away, but well below the scope of ion beam energy.
In above-mentioned purification, the laser ablation process that damageability is little, suitable for making control impurity is sneaked into, the nanostructure of composition, crystallinity etc.This situation is made nanostructure in order to use laser ablation method, and target material preferably can absorb the Wavelength of Laser scope of light source.
Fig. 3 is the figure that is illustrated in the nanostructure producing device that uses in the making of manganese oxide structure of the present invention.Use the manganese monoxide sintered body target, with He gas and oxygen (O herein,
2) mist of gas is as atmosphere gas, carries out laser ablation, the situation that making is had a manganese oxide structure of dendritic crystal body structure shown in Figure 1 describes thus.
Among Fig. 3, the metal system reative cell of reference marks 301 expression configuration targets.In the bottom of reative cell 301, be provided with reative cell 301 is carried out exhaust, make the ultravacuum gas extraction system 302 that forms ultrahigh vacuum in the reative cell 301.In the reative cell 301, gas introduction tube line 304 from atmosphere gas to reative cell 301 that supply with is installed.On this gas introduction tube line 304, mass flow controller 303a, the 303b of control to the flow of the atmosphere gas of reative cell 301 supplies is installed.In addition, in the bottom of reative cell 301, be provided with the gas exhaust system 305 that the atmosphere gas in the reative cell 301 is carried out differential exhaust.
In reative cell 301, dispose the target support 306 that keeps target 307.In this target support 306 rotating shaft is installed.This rotating shaft rotates under the control of not shown rotation control part, and target 307 rotates (8 rev/mins) thereupon.Relatively dispose accumulation substrate 309 with the surface of this target 307.The material that utilizes the laser irradiation to excite and break away from, penetrate from target 307 is stacked on this accumulation substrate 309.Use manganese monoxide (MnO) polycrystalline sintered body target (purity 99.9%) as target this moment.
In the embodiment 1, target 307 and accumulation substrate 309 form coaxial (on-axis) states.This in following embodiment 2,3 too.With reference to Fig. 9 " coaxial (on-axis) " and " from axle (off-axis) " is described on one side on one side.Fig. 9 (a) is " coaxial (on-axis) " state, and Fig. 9 (b) is " from axle (off-axis) " state.Shown in Fig. 9 (a), under " coaxial (on-axis) " state, target 307 and accumulation substrate 309 are parastate.In other words, under " coaxial (on-axis) " state, the normal 307a of target 307 (that is the line on vertical flat target 307 surfaces) forms parallel shape with the normal 309a (lines on vertical flat accumulation substrate 309 surfaces) that piles up substrate 309.
And shown in Fig. 9 (b), under " from axle (off-axis) " state, target 307 and accumulation substrate 309 are not parastate.In other words, under " from axle " state, the normal 307a of target 307 line of flat target 307 surfaces (that is, perpendicular to) does not form parallel shape with the normal 309a (lines on vertical flat accumulation substrate 309 surfaces) that piles up substrate 309.
In order to obtain the nanostructure with dendritic crystal body structure of the present invention, must be under " coaxial (on-axis) " state.As explanation in following comparative example 3, because " from axle (off-axis) " state can not get desired nanostructure with dendritic crystal body structure.
In the outside of reative cell 301, dispose to the pulsed laser source 308 of target 307 irradiations as the laser of energy light beam.The top of reative cell 301 is equipped with the laser that imports laser in reative cell 301 and imports window 310.On the laser optical path that penetrates by pulsed laser light source 308, dispose slit 311, lens 312 and speculum 313 successively from pulsed laser light source 308, the laser that penetrates from pulsed laser light source 308 imports window 310 by laser and is radiated on the target 307 that is arranged in the reative cell 301 by slit 311 shaping, by lens 312 light harvestings, by speculum 313 reflections.
Work to nanostructure producing device with said structure describes.Utilization with reative cell 301 inside, is drawn into vacuum 1.0 * 10 based on the ultrahigh vacuum gas extraction system 302 of turbomolecular pump
-6About pa, after the exhaust,, import He gas and O by gas introduction tube line 304 via mass flow controller 303a and 303b
2Gas.In addition, as mass flow, the He conductance is gone into 495.5sccm, O
2Conductance is gone into 0.5sccm (therefore, O
2Gas is 0.1% to the mass flow ratio of He gas).Here, by with gas blow-off system 305 operations linkages based on vortex pump or helicla flute pump, the pressure of the atmosphere rare gas in the reative cell 101 is set at the particular pressure value of the scope about 13.33～1333Pa.
Under this state, by pulsed laser light source 308, to be configured on the target support 306 with free-wheeling system, purity is on the surface of many crystallizations of MnO sintered body target 307 of 99.9%, irradiating laser.At this moment, use argon fluorine (ArF) excimer laser (wavelength: 193nm, pulse width: 12ns, pulse energy: 50mJ, energy density: 1J/cm
2, frequency repeatedly: 10Hz).At this moment, on MnO target 307 surfaces, produce the laser ablation phenomenon, and the ion or the neutral particle (atom, molecule, Particle Cluster etc.) that break away from Mn, O, MnO etc., ion has first kinetic energy 50eV, neutral particle has first kinetic energy 5eV, and the size of mainly keeping molecule, Particle Cluster on the normal direction of target penetrates.Then, break away from material by colliding with the atmosphere rare-gas atom, it is disorderly and unsystematic that heading becomes, and kinetic energy is dissipated in the atmosphere gas simultaneously, piles up to be nanostructure on the distance relative accumulation substrate 309 of about 35mm.In addition, substrate and target temperature all do not have positive control.
At this moment, as atmosphere gas, though used O
2The mist of gas and He gas, but can use Ar, Kr, Xe, N
2Wait other inert gases to replace He.In this case, can setting pressure, make gas density and He gas and O
2The mist situation of gas is the same.
To utilizing said method, with the He gas and the O of atmosphere gas
2The mixture pressure of gas is taken as the 662Pa with He gas 667Pa homogenous quantities, and the Mn oxide of piling up between 1000 seconds carries out the evaluation of fine structure.
As shown in Figure 1 and Figure 2, the Mn oxide of Dui Jiing is agglomerated into the dendritic crystal body structure of highly about 7.5 μ m by the primary particle with high crystalline of several nm of minimum component unit, and forms nanostructure as can be known.
As above-mentioned, utilize the manganese oxide structure preparation method of embodiment 1, can produce and have (forming) manganese oxide structure by the coalescent dendritic crystal body structure that forms of primary particle by the minimum component unit of the particle shape with high crystalline.
Target material is not limited in many crystallizations of manganese monoxide sintered body, also can use the Mn oxide of different valence state such as manganese sesquioxide managnic oxide, mangano-manganic oxide, can certainly use the single crystals target.
(embodiment 2)
In embodiment 2, obtain utilizing the condition (specifically being the pressure difference of mass flow and mist) different, by Mn oxide (MnO with embodiment 1
x) nanostructure that forms and preparation method thereof describes.
Fig. 4 is the electron scanning micrograph of the manganese oxide structure in embodiment 2.Manganese oxide structure, clear and definite as the top figure among Fig. 4, primary particle is coalescent as can be known, forms the secondary structure of hundreds of nm.As from the sectional view of Fig. 4 clear and definite, secondary structure has the dendritic crystal body structure of highly about 14 μ m as can be known.And then, from the TEM photo of Fig. 5 clear and definite, primary particle is the particle about the very high several～10nm of the crystallinity that can obviously confirm of lattice as can be known.
Manganese oxide structure with dendritic crystal body structure as shown in Figure 4 except following some, can utilize the preparation method identical with embodiment 1 to make.That is, in embodiment 2, as mass flow, the He conductance is gone into 499sccm, O
2Conductance is gone into 1.0sccm (therefore, O
2Gas reaches 0.20% to the mass flow ratio of He gas).He and O
2Mixture pressure, be taken as 657Pa with He gas 667Pa homogenous quantities.
The Mn oxide of piling up, as Fig. 4, shown in Figure 5, (minimal structure unit is several～10nm have a high crystalline) coalescent dendritic crystal body structure that forms highly about 14 μ m of primary particle forms nanostructure as can be known.
(embodiment 3)
In embodiment 3, to utilize that the condition (concrete, mass flow with mixture pressure different) different with embodiment 1 and embodiment 2 obtain by Mn oxide (MnO
x) nanostructure that forms and preparation method thereof describes.
Fig. 6 is the electron scanning micrograph of the manganese oxide structure in the present embodiment.Manganese oxide structure, as the top figure of Fig. 6 clear and definite, primary particle is coalescent as can be known, forms the offspring about a few μ m.As from the sectional view of Fig. 6 clear and definite, secondary structure has the dendritic crystal body structure of highly about 2.5 μ m as can be known.And then from the TEM photo of Fig. 7 clear and definite, primary particle is crystalline very high several～10nm left and right sides particle that lattice can obviously be confirmed as can be known.
Manganese oxide structure with dendritic crystal body structure shown in Figure 6 except following some, can utilize the preparation method identical with embodiment 1 to make.That is, in embodiment 3, as mass flow, the He conductance is gone into 497.5sccm, O
2Conductance is gone into 2.5sccm (therefore, O
2Gas reaches 0.50% to the mass flow ratio of He gas).In addition, the pressure of He gas is taken as the 644Pa with He gas 667Pa homogenous quantities.
The Mn oxide of piling up as Fig. 6, shown in Figure 7, is coalescent highly about 2.5 μ m dendritic crystal body structures, the formation nanostructure of forming of the primary particle with high crystalline of several～10nm by minimum component unit as can be known.
Embodiment
Below enumerate embodiment and comparative example, illustrate in greater detail the present invention.
Embodiment 1
The manganese oxide structure that will have the dendritic crystal body structure that is formed by the emboliform minimum component unit with high crystalline shown in Figure 4 is made test electrode as catalyst material.
Test electrode can be made in the following order.At first, use the method for explanation in the embodiment 1, as Figure 11 pattern be illustrated on the vitreous carbon of Φ 3mm,, directly pile up the manganese oxide structure with dendritic crystal body structure of (carry and hold) about 14 μ m thickness (height) by having the mask of Φ 2mm opening.The catalyst of test electrode carries the portion of holding, and as shown in figure 12, is that the vitreous carbon that will grind to form the Φ 3mm of minute surface is pressed into the structure that is cut in the externally threaded PEEK material of 6mm on every side.Then, carry the portion of holding and be screwed into as shown in figure 12 in the electrode body, utilize to electrically contact and carries out waterproof with encapsulant with directly carrying the catalysis of having held manganese oxide structure with dendritic crystal body structure.By the Φ 1.6mm brass bar of electrode body, draw electric current from test electrode.
The test electrode that use is made with said method is estimated the hydrogen reduction catalytic capability by the cyclic voltammetry of three utmost point electrolytic cells.Evaluation as working electrode, makes the oxygen dissolving saturated with test electrode in the potassium hydroxide aqueous solution (pH value 13) of 0.1mol/L, implements under the oxygen atmosphere.In this case, with platinum filament as to electrode, with silver/silver chloride electrode as reference electrode.
Figure 13 represents cyclic voltammogram.Among Figure 13, be represented by dotted lines the comparison electrode 1 that does not carry the just vitreous carbon of holding manganese oxide structure and represent to carry the comparison electrode 2 of the mangano-manganic oxide body of powder of having held micron-scale with dotted line, by comparing, hold in the test electrode of the manganese oxide structure with dendritic crystal body structure carrying of representing with solid line, current density has increased about 5.8 times (to electrodes 1 relatively) and about 2.4 times (to electrode 2 relatively) in maximum.Relatively near the hydrogen reduction current potential of the maximum current density the expression-0.4V in the electrode 1 and 2 is opposite with it, near the superpotential-0.2V less than about 0.2V, observes the hydrogen reduction current potential that shows maximum current density.
Think by with the Mn oxide of catalyst as the manganese nanostructure of the present invention that contains by the coalescent dendritic crystal body structure that forms of the primary particle with high crystalline, thereby realize The above results.Although about 14 μ m catalyst layer has as thin as a wafer also been realized very high hydrogen reduction catalytic capability.
Comparative example 1
(making dendritic crystal body structure nanostructure in addition)
Fig. 8 is the electron scanning micrograph of manganese oxide structure in the comparative example 1.
Manganese oxide structure shown in Figure 8 except that following some, utilize the preparation method identical with embodiment 1 and obtains.That is, in comparative example 1, as mass flow, the He conductance is gone into 500.0sccm, O
2Conductance is gone into 0.0sccm (therefore, O
2Gas reaches 0.00% to the mass flow ratio of He gas).In addition, the pressure of He gas is 667Pa.
The Mn oxide of piling up, as shown in Figure 8, primary particle is agglomerated into highly about 650nm column structure as can be known, forms nanostructure.That is, do not import O
2During gas, even coaxial (on-axis) state also can not get having the manganese oxide structure of dendritic crystal body structure.
In the cyclic voltammogram that the cyclic voltammetry by similarly to Example 1 condition forms, near 0.4V, observe the hydrogen reduction current potential.
Comparative example 2
With mass flowmenter, the He conductance is gone into 495.0sccm, O
2Conductance is gone into 5.0sccm (therefore, O
2Gas reaches 1.00% to the mass flow ratio of He gas).He and O
2Mixture pressure be taken as beyond the 623Pa with He gas 667Pa homogenous quantities, the same with embodiment 1, obtain manganese oxide structure.The manganese oxide structure that obtains as shown in figure 10, has the structure as cotton candy, and does not have the dendritic crystal body structure.
In addition, utilizing in the cyclic voltammogram that cyclic voltammetry forms of the condition the same with embodiment 1 observes the hydrogen reduction current potential near 0.4V.
Comparative example 3
Except the relation with target 307 and accumulation substrate 309 makes into from axle (off-axis) state (with reference to Fig. 9 (b)), obtain manganese oxide structure equally with embodiment 1, piling up on the substrate 309, form single film by Mn oxide, but can not get desired manganese oxide structure with dendritic crystal body structure.
Utilizability on the industry
Manufacture method of the present invention, can provide have excellent hydrogen reduction catalytic capability, applicable In oxygen reduction electrode, gas sensor etc., has the transiting metal oxidation of dendritic crystal body structure The thing nanostructure.
Oxygen reduction electrode of the present invention has excellent hydrogen reduction catalytic capability, for example can be used as The oxygen utmost point of air zinc battery, fuel cell etc.
Claims
(according to the modification of the 19th of treaty)
1. the manufacture method of a manganese oxide structure, this manganese oxide structure has by the coalescent dendritic crystal body structure that forms of primary particle, it is characterized in that:
As atmosphere gas, the ratio of oxygen is counted more than 0.05% below 0.5% with mass flow ratio in the described atmosphere gas with the mist of inert gas and oxygen,
Have: in described atmosphere gas, by laser being radiated on the target plate that forms by Mn oxide, the constitute of target plate is broken away from, and make this disengaging material be deposited in described target plate almost parallel opposing substrates on, obtain described operation with manganese oxide structure of dendritic crystal body structure.
2. manufacture method as claimed in claim 1 is characterized in that:
Using with described manganese oxide structure as working electrode, with platinum as to electrode, with silver/silver chlorate as reference electrode, and in the cyclic voltammogram that obtains as the cyclic voltammetry of three utmost point electrolytic cells of electrolyte with the potassium hydroxide solution of concentration 0.1mol/L and pH value 13, near-0.2V, show the hydrogen reduction current potential.
3. manufacture method as claimed in claim 1 is characterized in that:
Described inert gas is a helium.
4. manufacture method as claimed in claim 1 is characterized in that:
By providing energy to make its activation to atmosphere gas.
5. manufacture method as claimed in claim 1 is characterized in that:
Described atmosphere gas has the following pressure of the above 1333Pa of 13.33Pa.
6. manufacture method as claimed in claim 1 is characterized in that:
Described laser is the pulse laser with the following pulse width of the above 20ns of 5ns.
7. manufacture method as claimed in claim 1 is characterized in that:
Described laser has 0.5J/cm
2Above 2J/cm
2Following energy density.
8. manufacture method as claimed in claim 1 is characterized in that:
Described target plate is the sintered body of Mn oxide.
9. manufacture method as claimed in claim 1 is characterized in that:
Has the operation that the manganese oxide structure that obtains is further heated.
10. manufacture method as claimed in claim 1 is characterized in that:
The pressure of described atmosphere gas is changed.
11. manufacture method as claimed in claim 1 is characterized in that, has:
Before described operation, in advance described target plate and substrate are oppositely arranged in parallel to each other the operation in the reaction system.
12. manufacture method as claimed in claim 1 is characterized in that, has:
For by control the size that is formed near the HTHP zone the described target plate to described target plate illuminating laser beam, to 1) atmosphere gas pressure and 2) at least one operation of adjusting of distance of described target plate and substrate.
13. an oxygen reduction electrode contains: have transition metal oxide nano structure, it is characterized in that by the coalescent dendritic crystal body structure that forms of primary particle,
Described migration metal is a manganese,
Described primary particle has the following average grain diameter of the above 20nm of 2nm.
(14. deletion)
(15. deletion)
16. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described dendritic crystal body structure has the following average height of the above 20 μ m of 1 μ m.
17. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described primary particle has the following average grain diameter of the above 20nm of 2nm, and described dendritic crystal body structure has the following average height of the above 20 μ m of 1 μ m.
18. an oxygen reduction electrode contains: have transition metal oxide nano structure, it is characterized in that by the coalescent dendritic crystal body structure that forms of primary particle,
Using with described electrode as working electrode, with platinum as to electrode, with silver/silver chlorate as reference electrode, and in the cyclic voltammogram that obtains as the cyclic voltammetry of three utmost point electrolytic cells of electrolyte with the potassium hydroxide aqueous solution of concentration 0.1mol/L and pH value 13, show the hydrogen reduction current potential near-0.2V, described migration metal is a manganese.
(19. deletion)
20. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described transition metal oxide nano structure is at least a transition metal oxide that is selected from an oxidation transition metal, four oxidations, three transition metal, three oxidations, two transition metal and the titanium dioxide transition metal.
21. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described transition metal oxide nano structure is at least a Mn oxide that is selected from manganese monoxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and the manganese dioxide.
22. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described transition metal oxide nano structure is formed on the conductive base material.
23. oxygen reduction electrode as claimed in claim 18 is characterized in that:
Described cyclic voltammogram shows the hydrogen reduction current potential in-scope below the above 0V of 0.25V.
(24. deletion)
25. oxygen reduction electrode as claimed in claim 18 is characterized in that:
Described migration metal oxide nanostructure body is at least a migration metal oxide that is selected from oxidation migration metal, four oxidations, three migration metals, three oxidations, two migration metals and titanium dioxide migration metal.
26. oxygen reduction electrode as claimed in claim 18 is characterized in that:
Described migration metal oxide nanostructure body is at least a Mn oxide that is selected from manganese monoxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and manganese dioxide.
27. oxygen reduction electrode as claimed in claim 18 is characterized in that:
Described migration metal oxide nanostructure body is formed on the conductive base material.
Claims (24)
1. the manufacture method of a manganese oxide structure, this manganese oxide structure has by the coalescent dendritic crystal body structure that forms of primary particle, it is characterized in that:
As atmosphere gas, the ratio of oxygen is counted more than 0.05% below 0.5% with mass flow ratio in the described atmosphere gas with the mist of inert gas and oxygen,
Have: in described atmosphere gas, by laser being radiated on the target plate that forms by Mn oxide, the constitute of target plate is broken away from, and make this disengaging material be deposited in described target plate almost parallel opposing substrates on, obtain described operation with manganese oxide structure of dendritic crystal body structure.
2. manufacture method as claimed in claim 1 is characterized in that:
Using with described manganese oxide structure as working electrode, with platinum as to electrode, with silver/silver chlorate as reference electrode, and in the cyclic voltammogram that obtains as the cyclic voltammetry of three utmost point electrolytic cells of electrolyte with the potassium hydroxide solution of concentration 0.1mol/L and pH value 13, near-0.2V, show the hydrogen reduction current potential.
3. manufacture method as claimed in claim 1 is characterized in that:
Described inert gas is a helium.
4. manufacture method as claimed in claim 1 is characterized in that:
By providing energy to make its activation to atmosphere gas.
5. manufacture method as claimed in claim 1 is characterized in that:
Described atmosphere gas has the following pressure of the above 1333Pa of 13.33Pa.
6. manufacture method as claimed in claim 1 is characterized in that:
Described laser is the pulse laser with the following pulse width of the above 20ns of 5ns.
7. manufacture method as claimed in claim 1 is characterized in that:
Described laser has 0.5J/cm
2Above 2J/cm
2Following energy density.
8. manufacture method as claimed in claim 1 is characterized in that:
Described target plate is the sintered body of Mn oxide.
9. manufacture method as claimed in claim 1 is characterized in that:
Has the operation that the manganese oxide structure that obtains is further heated.
10. manufacture method as claimed in claim 1 is characterized in that:
The pressure of described atmosphere gas is changed.
11. manufacture method as claimed in claim 1 is characterized in that, has:
Before described operation, in advance described target plate and substrate are oppositely arranged in parallel to each other the operation in the reaction system.
12. manufacture method as claimed in claim 1 is characterized in that, has:
For by control the size that is formed near the HTHP zone the described target plate to described target plate illuminating laser beam, to 1) atmosphere gas pressure and 2) at least one operation of adjusting of distance of described target plate and substrate.
13. an oxygen reduction electrode is characterized in that, contains:
Has transition metal oxide nano structure by the coalescent dendritic crystal body structure that forms of primary particle.
14. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described transition metal is a manganese.
15. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described primary particle has the following average grain diameter of the above 20nm of 2nm.
16. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described dendritic crystal body structure has the following average height of the above 20 μ m of 1 μ m.
17. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described primary particle has the following average grain diameter of the above 20nm of 2nm, and described dendritic crystal body structure has the following average height of the above 20 μ m of 1 μ m.
18. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Using with described electrode as working electrode, with platinum as to electrode, with silver/silver chlorate as reference electrode, and in the cyclic voltammogram that obtains as the cyclic voltammetry of three utmost point electrolytic cells of electrolyte with the potassium hydroxide aqueous solution of concentration 0.1mol/L and pH value 13, near-0.2V, show the hydrogen reduction current potential.
19. oxygen reduction electrode as claimed in claim 18 is characterized in that:
Described transition metal is a manganese.
20. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described transition metal oxide nano structure is at least a transition metal oxide that is selected from an oxidation transition metal, four oxidations, three transition metal, three oxidations, two transition metal and the titanium dioxide transition metal.
21. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described transition metal oxide nano structure is at least a Mn oxide that is selected from manganese monoxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and the manganese dioxide.
22. oxygen reduction electrode as claimed in claim 13 is characterized in that:
Described transition metal oxide nano structure is formed on the conductive base material.
23. oxygen reduction electrode as claimed in claim 18 is characterized in that:
Described cyclic voltammogram shows the hydrogen reduction current potential in-scope below the above 0V of 0.25V.
24. oxygen reduction electrode as claimed in claim 23 is characterized in that:
Described transition metal is a manganese.
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|---|---|---|---|
| JP2004044265 | 2004-02-20 | ||
| JP044265/2004 | 2004-02-20 | ||
| JP176813/2004 | 2004-06-15 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101984773A (en) * | 2007-07-31 | 2011-03-09 | 昭和电工株式会社 | Metal oxide electrode catalyst, use thereof, and method for producing metal oxide electrode catalyst |
| CN104658763A (en) * | 2015-01-21 | 2015-05-27 | 西北大学 | Manganese dioxide dendritic nano array electrode material and preparation method |
| CN107999076A (en) * | 2017-12-11 | 2018-05-08 | 北京化工大学 | It is a kind of that there are Hexagonal voids and be rich in the metal composite oxide nanometer sheet of Lacking oxygen, preparation method and use |
| US20210123151A1 (en) * | 2017-12-14 | 2021-04-29 | Riken | Manganese oxide for water oxidation catalyst, manganese oxide/carbon mixture, manganese oxide composite electrode material, and their production methods |
-
2005
- 2005-02-16 CN CNB2005800003808A patent/CN100567138C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101984773A (en) * | 2007-07-31 | 2011-03-09 | 昭和电工株式会社 | Metal oxide electrode catalyst, use thereof, and method for producing metal oxide electrode catalyst |
| CN101984773B (en) * | 2007-07-31 | 2014-09-10 | 昭和电工株式会社 | Metal oxide electrode catalyst, use thereof, and method for producing metal oxide electrode catalyst |
| CN104658763A (en) * | 2015-01-21 | 2015-05-27 | 西北大学 | Manganese dioxide dendritic nano array electrode material and preparation method |
| CN104658763B (en) * | 2015-01-21 | 2017-03-15 | 西北大学 | A kind of manganese dioxide dendroid nano-array electrode material and preparation method |
| CN107999076A (en) * | 2017-12-11 | 2018-05-08 | 北京化工大学 | It is a kind of that there are Hexagonal voids and be rich in the metal composite oxide nanometer sheet of Lacking oxygen, preparation method and use |
| US20210123151A1 (en) * | 2017-12-14 | 2021-04-29 | Riken | Manganese oxide for water oxidation catalyst, manganese oxide/carbon mixture, manganese oxide composite electrode material, and their production methods |
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|---|---|
| CN100567138C (en) | 2009-12-09 |
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