CN101733095B - Catalyst for water electrolysis and preparation and application thereof - Google Patents
Catalyst for water electrolysis and preparation and application thereof Download PDFInfo
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- CN101733095B CN101733095B CN2008102287087A CN200810228708A CN101733095B CN 101733095 B CN101733095 B CN 101733095B CN 2008102287087 A CN2008102287087 A CN 2008102287087A CN 200810228708 A CN200810228708 A CN 200810228708A CN 101733095 B CN101733095 B CN 101733095B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to an anode catalyst used for a water electrolysis device of solid polymer electrolyte. The molecular formula of the catalyst is IrxRu1-xMyOz, wherein x is more than 0 and not more than 1, y is more than 0 and not more than 0.3, z is more than 1.5 and not more than 2.9, and M is one or more of such transition metals as Mo, W and Cr. In terms of the gross weight of the catalyst, the weight ratio of M in the catalyst is less than 10wt%. The required catalyst is characterized in that addition of the third component (or the fourth component) reduces the microcrystal grains of the catalyst, enlarges the specific surface area of the catalyst and improves the catalytic activity of the catalyst. The catalyst has lower overpotential and long life when serving as the anode catalyst in an SPE water electrolysis cell. The catalyst is used for the electrodes for oxygen evolution of the SPE water electrolysis cell, catalyst-membrane assemblies (CCM), membrane-electrode assemblies (MEA), regenerative fuel cells (RFC) and sensors.
Description
Technical field
The present invention relates to solid polymer electrolyte (Solid Polymer Electrolyte; SPE) water electrolysis anode catalyst, specifically a kind of effective catalyst that can be applicable to system oxygen electrode in SPE water electrolysis, renewable formula fuel cell or the various electrolysis application.
Background technology
Hydrogen is a kind of cleaning, energy carrier efficiently, and it has renewable, free of contamination characteristics.Water electrolysis prepares the important means that hydrogen is hydrogen manufacturing, is a kind of very technology of ripe preparation High Purity Hydrogen.It is at present normal that what adopt is the alkaline water electrolytic technology, but exist liquid electrolyte to run off easily, shortcoming such as equipment is perishable.The solid electrolyte water electrolysis possesses tangible advantage than traditional alkaline water electrolytic, for example higher security reliability, higher energy efficiency, and also the hydrogen purity that is prepared by the SPE water electrolytic cell can be higher than 99.99%.These advantages make the SPE water electrolysis become the research focus of hydrogen producing technology in recent years.
Solid electrolyte film commonly used is that (ProtonExchange Membrane, PEM), its water electrolysis process is the converse process of Proton Exchange Membrane Fuel Cells reaction to PEM in the SPE water electrolysis at present.This electrolytic cell device structure is similar to Proton Exchange Membrane Fuel Cells, but works in a different manner.In the SPE water electrolysis; On the electrolytic cell in addition voltage and feed pure water after; Oxygen evolution reaction (Oxygen Evolution Reaction takes place on anode; OER) and discharge oxygen, the reduction of proton takes place on negative electrode and discharge hydrogen (Hydrogen Evolution Reaction, HER).Electrolyte is both as the medium of leading proton, again as the barrier film of isolating hydrogen, carrier of oxygen.
In the electrolytic process, main activation polarization results from the electrochemical process of anode.Researcher's work also concentrates on increases the anode catalyst activity with the aspect that cuts down the consumption of energy.IrO
2Be a kind of good OER catalyst, and in acidic electrolyte bath, have fabulous stability.RuO
2Have higher OER electro catalytic activity, but in acid solution, RuO
2Heavy corrosion can take place.
Think RuO with Stucki
2The reason that is corroded is RuO in the OER process
2Be oxidized into the RuO of solubility
4[R.
, S.Stucki, J.Electroanal Chem, 172 (1984) 211].IrO
2And RuO
2Often be made into compound as the water electrolysis anode catalyst, active and stable preferably to obtain.Increase the focus that Ir-Ru oxide anode activity of such catalysts becomes present research through adding the 3rd component (or the 4th component).
US2003/0057088A1 relates to the SPE apparatus for electrolyzing that uses Ir-Ru oxide anode catalyst, and said catalyst contains the metal oxide of at least a chosen from Fe (Fe), nickel (Ni) and cobalt (Co).The main purpose of doping iron (Fe), nickel (Ni) and cobalt (Co) is in order to strengthen the durability of Ir-Ru oxide anode catalyst, obviously not improve aspect the catalyst activity.
People such as A.Mashall have prepared Ir
xRu
yTa
zO
2[International Journal of HydrogenEnergy32 (2007) 2320], Ir thought in article
0.6Ru
0.4O
2At Ir
xRu
yTa
zO
2In have best catalytic activity, the adding of Ta does not obviously increase the catalytic activity of catalyst.
People such as A.Mashall preparation is also studied the Ir that knows clearly
xRu
ySn
zO
2[Russian Journal ofElectrochemistry, 42 (2006) 1134], article think that the adding of the 3rd component S n has reduced the activity of such catalysts area, have increased the ohmage of catalyst, and when using it for the SPE water electrolysis, the electrolysis performance descends.
The related catalyst of patent CN1874841 comprises IrO
2With optional RuO
2With the inorganic oxide of high-specific surface area (like TiO
2, Al
2O
3, ZrO
2And composition thereof).This invents related inorganic oxide is high-specific surface area class and and IrO
2And RuO
2Active material forms mixture.The inorganic oxide that adds high-specific surface area is in order to increase the decentralization of active material, still can not to reduce IrO
2And RuO
2Particle; And the inorganic oxide that is added is semiconductor or insulator, caused the decline of catalyst monolithic conductive property.
Summary of the invention
The objective of the invention is to provide a kind of anode catalyst of the improved SPE of being used for apparatus for electrolyzing, this catalyst based on metal oxide containing precious metals (like IrO
2, RuO
2) yttrium oxide and be doped into other element (Mo, W, one or more among the Cr) particularly.In course of reaction, the 3rd component of being mixed (or the 4th component) element can play and suppress IrO
2Or IrO
2, RuO
2The effect that the compound crystallite is grown up.And the 3rd (the 4th) constituent content is very low in catalyst, and is the amorphous state existence, and catalyst activity is not almost had adverse effect.This catalyst has littler microcrystal grain, higher catalytic activity than containing transition metal element procatalyst not.When they are used for the SPE apparatus for electrolyzing, the low oxygen overpotential of analysing is arranged, low noble metal loading and long-life, and can make the SPE apparatus for electrolyzing that high durability is arranged.
The Adams fusion method that this Preparation of catalysts method is a kind of modulation, preparation technology's flow process is simple, and the waste gas that produces in the reaction feeds NaOH alkali lye and reclaims, whole process of preparation safety, environmental protection.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
A kind of catalyst for water electrolysis, useful molecules formula Ir
xRu
1-xM
yO
zExpression, wherein 0<x≤1,0<y≤0.3,1.5<z≤2.9, wherein M is Mo, W, one or more among the Cr.
The ratio that said M accounts for the catalyst gross weight greater than 0wt%, is preferably 2～6wt% less than 10wt%, and the best is 2.73～5wt%.
Concrete preparation process is:
(1) by required metering ratio; The solubility precursor compound of yttrium oxide, ruthenium-oxide and the solubility precursor compound of doped chemical M are dissolved in deionized water; The molar concentration of the precursor compound of above-mentioned yttrium oxide, ruthenium-oxide and M in deionized water is 2～3mol/l; Using alkali to regulate pH value is 7～8, obtains solution A;
(2) in A, add alkali-metal nitrate (KNO
3, NaNO
3, LiNO
3), under the stirring in 60～80 ℃ of water-baths evaporate to dryness, obtain mixture B;
(3) with mixture B dry 6～24h in 60～80 ℃ of baking ovens, 350～600 ℃ of roasting 0.5～1h obtain pressed powder C in the air, and reaction generates waste gas and imports NaOH alkali lye;
(4) pressed powder C is spent deionised water and be placed on 60～80 ℃ of oven dry in the vacuum drying oven, obtain catalyst of the present invention.
Iridium involved in the present invention is mainly tetravalence iridium (Ir
4+), but also possibly have a certain proportion of trivalent iridium (Ir
3+).Ruthenium can be tetravalence ruthenium (Ru
4+), but also can have a small amount of trivalent ruthenium (Ru
3+); Doped chemical is selected from one or more in molybdenum (Mo), tungsten (W), the chromium (Cr).The contained transition metal weight ratio of catalyst related among the present invention is lower than 10wt% greater than 0wt%.
A certain amount of catalyst, optional ionomer material and suitable solvent (like isopropyl alcohol) are mixed into the slurry of homogeneous through sonic oscillation; Through the method for spraying, printing, curtain coating slurry is deposited to uniformly the both sides of Nafion1035 film then; Treat to process the thin layer Catalytic Layer after the isopropyl alcohol volatilization, obtain film-catalyst assembly (CCM) after the hot pressing.Prepared CCM is sandwiched between two carbon papers, and as outside seal, hot pressing prepares film forming-electrode three-in-one component (MEA) with the polyester frame.Anode-side adopts catalyst according to the invention, and loading is 0.5～3mg/cm
2At cathode side, use Pt catalyst (like Pt/C or Pt black (Pt Black)), loading is 0.1～1mgPt/cm
2
Advantage of the present invention is mainly reflected in:
1, is doped into the microcrystal grain that can reduce catalyst behind the 3rd component (or the 4th component) transition metal, increases the specific area of catalyst, increase activity of such catalysts.Than other the 3rd (the 4th) component doped catalyst, catalyst according to the invention is compound (homogeneous phase), and doping component content is low; And mostly the said catalyst of other related invention is mixture, thereby doping component becomes to have influenced mutually catalytic activity separately.
2, effect is good.Experiment showed, under same current density when adopting catalyst according to the invention to be used for SPE apparatus for electrolyzing anode result of use be superior to the not mixing catalyst of element according to the invention.Lower specific energy consumption is arranged during the production unit volume of hydrogen, under same current density, have lower decomposition voltage.Catalyst I r for example
0.4Ru
0.6O
2During as the water electrolytic cell anode catalyst, at 1000mA/cm
2Under decomposition voltage be 1.646V; And the later catalyst I r of Mo that mixed
0.4Ru
0.6Mo
0.05O
2.15During as the water electrolytic cell anode catalyst, 1000mA/cm
2Following decomposition voltage is 1.606V; The later catalyst I r of W has mixed
0.4Ru
0.6W
0.03O
2.09During as the water electrolytic cell anode catalyst, 1000mA/cm
2Following decomposition voltage is 1.598V.
3, preparation technology is simple, and the waste gas that produces in the reaction reclaims through NaOH alkali lye.Safe preparation process, environmental protection.
Description of drawings
Fig. 1 is Ir of the present invention
0.4Ru
0.6Mo
0.05O
2.15With Ir before the Mo that do not mix
0.4Ru
0.6O
2The XRD figure contrast.XRD figure shows that both are the crystalline texture of rutile phase, uses the Scherrer formula to calculate the catalyst crystallite particle size and is respectively Ir
0.4Ru
0.6Mo
0.05O
2.15: 2nm; Ir
0.4Ru
0.6O
2: 4.1nm.
Fig. 2 is Ir of the present invention
0.4Ru
0.6Mo
0.05O
2.15With Ir before the Mo that do not mix
0.4Ru
0.6O
2At 0.5MH
2SO
4Cyclic voltammetric in the solution (CV) figure contrast.Its electrode preparation method is following: with the Nafion solution blending of 1ml isopropyl alcohol, 5mg catalyst and 50 μ L5wt%, sonic oscillation mixed it in 30 minutes; Use microsyringe coating 25 μ L slurries on the glass-carbon electrode and in air, drying.Test is carried out in the three-electrode system of a standard, uses Pt sheet as to electrode, and with saturated calomel electrode (SCE) as reference electrode.Test was carried out behind the high pure nitrogen in feeding in 30 minutes.Test result shows the active raising of doping Mo rear catalyst.
Fig. 3 is Ir of the present invention
0.4Ru
0.6Mo
0.05O
2.15With Ir before the Mo that do not mix
0.4Ru
0.6O
2Single pond polarization curve comparison diagram during respectively as SPE water electrolysis anode catalyst.Wherein, negative electrode adopts the Japanese Tanaka commercial catalyst 28.4wt%Pt/C of company; Anode catalyst load amount is 1.5mg/cm
2, negative electrode load amount is 0.5mg/cm
2Adopt commercialization Nafion1035 film; The operating temperature of battery is 80 ℃.
Fig. 4 is Ir of the present invention
0.4Ru
0.6W
0.03O
2.09With Ir before the W that do not mix
0.4Ru
0.6O
2The XRD figure contrast.XRD figure is shown as the crystalline texture of rutile phase, uses the Scherrer formula to calculate the catalyst crystallite particle size and is respectively Ir
0.4Ru
0.6W
0.03O
2.09: 1.9nm; Ir
0.4Ru
0.6O
2: 4.1nm.
Fig. 5 is Ir of the present invention
0.4Ru
0.6W
0.03O
2.09With Ir before the W that do not mix
0.4Ru
0.6O
2At 0.5MH
2SO
4Cyclic voltammetric in the solution (CV) figure contrast.Method of testing is explained referring to Fig. 2.
Fig. 6 is Ir of the present invention
0.4Ru
0.6W
0.03O
2.09With Ir before the W that do not mix
0.4Ru
0.6O
2Polarization curve contrast in single pond during respectively as SPE water electrolytic cell anode catalyst.The monocell parameter is explained referring to Fig. 3.
Fig. 7 is the monocell polarization curve contrast of embodiments of the invention 3 and corresponding Comparative Examples.
Fig. 8 is the monocell polarization curve contrast of embodiments of the invention 4 and corresponding Comparative Examples.
Fig. 9 is the monocell polarization curve contrast of embodiments of the invention 5 and corresponding Comparative Examples.
Figure 10 is the monocell polarization curve contrast of embodiments of the invention 6 and corresponding Comparative Examples.
The specific embodiment
Adopt following examples and Comparative Examples explanation the present invention, but the present invention does not receive the restriction of following examples and Comparative Examples at present.
With 0.1617g chloro-iridic acid (H
2IrCl
66H
2O), 0.1147g ruthenic chloride (RuCl
32H
2O), 0.0943g molybdic acid (H
2MoO
4H
2O) be dissolved in the 50ml deionized water, wherein the Ir/Ru mol ratio is 2/3.Add 10g sodium nitrate (NaNO
3), stir and make its dissolving, adding 2MNaOH aqueous solution adjusting pH value then is 7.To mix back solution and place 80 ℃ of temperature stirred in water bath evaporates to dryness, place 60 ℃ of dry 12h of baking oven then.With the solid abrasive that obtains, place tube furnace then, rise to 350 ℃ with 10 ℃/minute earlier, rise to 450 ℃ with 5 ℃/minute again, and be incubated 0.5 hour down at 450 ℃.The adding deionized water dissolved DDGS after thing to be generated was cooled to room temperature, then with insoluble solids centrifugation-washing, behind the several separator was put into 60 ℃ of vacuum drying ovens dry 24 hours repeatedly, promptly obtained catalyst I r of the present invention
0.4Ru
0.6Mo
0.05O
2.15, the quality that obtains Mo through plasma spectrometer (ICP) analysis is 2.73wt% than content.
Comparative Examples 1
With 0.2432g chloro-iridic acid (H
2IrCl
66H
2O), 0.1725g ruthenic chloride (RuCl
32H
2O) be dissolved in the 50ml deionized water, wherein the Ir/Ru mol ratio is 2/3.Add 10g sodium nitrate (NaNO
3), stir and make its dissolving, adding 2MNaOH aqueous solution adjusting pH value then is 7.To mix back solution and place 80 ℃ of temperature stirred in water bath evaporates to dryness, place 60 ℃ of dry 12h of baking oven then.With the solid abrasive that obtains, place tube furnace then, rise to 350 ℃ with 10 ℃/minute earlier, rise to 450 ℃ with 5 ℃/minute again, and be incubated 0.5 hour down at 450 ℃.The adding deionized water dissolved DDGS after thing to be generated was cooled to room temperature, then with insoluble solids centrifugation-washing, behind the several separator was put into 60 ℃ of vacuum drying ovens dry 24 hours repeatedly, promptly obtained Comparative Examples one catalyst I r
0.4Ru
0.6O
2
As can beappreciated from fig. 1, catalyst of the present invention and Comparative Examples one catalyst are the rutile phase structure, calculate the catalyst crystallite particle size through the Scherrer formula and are respectively Ir
0.4Ru
0.6Mo
0.05O
2.15: 2nm; Ir
0.4Ru
0.6O
2: 4.1nm.The microcrystal grain size of catalyst of the present invention is less than the microcrystal grain size of Comparative Examples one catalyst.This possibly be because the Mo that is doped in catalyst preparation process at IrO
2-RuO
2The microcrystal grain surface has formed Ir-O-Mo, the Ru-O-Mo key, thus suppressed IrO
2-RuO
2Growing up of microcrystal grain.And unnecessary MoO
3Formed water miscible Na
2MoO
4Finally by flush away.
As can beappreciated from fig. 2, at 0.5MH
2SO
4Prepared catalyst Ir of the present invention in the solution
0.4Ru
0.6Mo
0.05O
2.15Electro-chemical activity is greater than catalyst I r in the Comparative Examples one
0.4Ru
0.6O
2
As can beappreciated from fig. 3, prepared catalyst Ir of the present invention
0.4Ru
0.6Mo
0.05O
2.15Monocell performance as anode catalyst is superior to catalyst I r in the Comparative Examples one
0.4Ru
0.6O
2Monocell performance as anode catalyst.
Embodiment 2
With 0.167g chloro-iridic acid (H
2IrCl
66H
2O), 0.1185g ruthenic chloride (RuCl
32H
2O), 0.1443g ammonium tungstate ((NH
4)
5H
5[H
2(WO
4)
6] H
2O) be dissolved in the 50ml deionized water, wherein the Ir/Ru mol ratio is 2/3.Add 10g sodium nitrate (NaNO
3), stir and make its dissolving, adding 2MNaOH aqueous solution adjusting pH value then is 7.To mix back solution and place 80 ℃ of temperature stirred in water bath evaporates to dryness, place 60 ℃ of dry 12h of baking oven then.With the solid abrasive that obtains, place tube furnace then, rise to 350 ℃ with 10 ℃/minute earlier, rise to 450 ℃ with 5 ℃/minute again, and be incubated 0.5 hour down at 450 ℃.The adding deionized water dissolved DDGS after thing to be generated was cooled to room temperature, then with insoluble solids centrifugation-washing, behind the several separator was put into 60 ℃ of vacuum drying ovens dry 24 hours repeatedly, promptly obtained catalyst I r of the present invention
0.4Ru
0.6W
0.03O
2.09
As can beappreciated from fig. 4, catalyst of the present invention and Comparative Examples one catalyst are the rutile phase structure, calculate the catalyst crystallite particle size through the Scherrer formula and are respectively Ir
0.4Ru
0.6W
0.03O
2.09: 1.9nm; Ir
0.4Ru
0.6O
2: 4.1nm.The microcrystal grain size of catalyst of the present invention is less than the microcrystal grain size of Comparative Examples one catalyst.
As can beappreciated from fig. 5, at 0.5MH
2SO
4Prepared catalyst Ir of the present invention in the solution
0.4Ru
0.6W
0.03O
2.09Electro-chemical activity is greater than catalyst I r in the Comparative Examples one
0.4Ru
0.6O
2
As can beappreciated from fig. 6, prepared catalyst Ir of the present invention
0.4Ru
0.6W
0.03O
2.09Monocell performance as anode catalyst is superior to catalyst I r in the Comparative Examples one
0.4Ru
0.6O
2Monocell performance as anode catalyst.
Embodiment 3
With 0.2394g chloro-iridic acid (H
2IrCl
66H
2O), 0.1698g ruthenic chloride (RuCl
32H
2O), 0.31g chromic nitrate (Cr (NO
3)
39H
2O) be dissolved in the 50ml deionized water, wherein the Ir/Ru mol ratio is 2/3.Add 10g sodium nitrate (NaNO
3), stir and make its dissolving, adding 2MNaOH aqueous solution adjusting pH value then is 7.To mix back solution and place 80 ℃ of temperature stirred in water bath evaporates to dryness, place 60 ℃ of dry 12h of baking oven then.With the solid abrasive that obtains, place tube furnace then, rise to 350 ℃ with 10 ℃/minute earlier, rise to 450 ℃ with 5 ℃/minute again, and be incubated 0.5 hour down at 450 ℃.The adding deionized water dissolved DDGS after thing to be generated was cooled to room temperature, then with insoluble solids centrifugation-washing, behind the several separator was put into 60 ℃ of vacuum drying ovens dry 24 hours repeatedly, promptly obtained catalyst I r of the present invention
0.4Ru
0.6Cr
0.12O
2.36
As can beappreciated from fig. 7, prepared catalyst Ir of the present invention
0.4Ru
0.6Cr
0.12O
2.36Monocell performance as anode catalyst is superior to catalyst I r in the Comparative Examples one
0.4Ru
0.6O
2Monocell performance as anode catalyst.
Embodiment 4
With 0.2264g chloro-iridic acid (H
2IrCl
66H
2O), 0.0715g ruthenic chloride (RuCl
32H
2O), 0.0879g molybdic acid (H
2MoO
4H
2O) be dissolved in the 50ml deionized water, wherein the Ir/Ru mol ratio is 3/2.Add 10g potassium nitrate (KNO
3), stir and make its dissolving, adding 0.5M ammoniacal liquor adjusting pH value then is 8.To mix back solution and place 80 ℃ of temperature stirred in water bath evaporates to dryness, place 80 ℃ of dry 12h of baking oven then.With the solid abrasive that obtains, place tube furnace then, rise to 350 ℃ with 10 ℃/minute earlier, rise to 550 ℃ with 5 ℃/minute again, and be incubated 1 hour down at 550 ℃.The adding deionized water dissolved DDGS after thing to be generated was cooled to room temperature, then with insoluble solids centrifugation-washing, behind the several separator was put into 60 ℃ of vacuum drying ovens dry 24 hours repeatedly, promptly obtained catalyst I r of the present invention
0.6Ru
0.4Mo
0.05O
2.15
Comparative Examples 2
With 0.3294g chloro-iridic acid (H
2IrCl
66H
2O), 0.1038g ruthenic chloride (RuCl
32H
2O) be dissolved in the 50ml deionized water, wherein the Ir/Ru mol ratio is 3/2.Add 10g potassium nitrate (KNO
3), stir and make its dissolving, adding 0.5M ammoniacal liquor adjusting pH value then is 8.To mix back solution and place 80 ℃ of temperature stirred in water bath evaporates to dryness, place 80 ℃ of dry 12h of baking oven then.With the solid abrasive that obtains, place tube furnace then, rise to 350 ℃ with 10 ℃/minute earlier, rise to 550 ℃ with 5 ℃/minute again, and be incubated 1 hour down at 550 ℃.The adding deionized water dissolved DDGS after thing to be generated was cooled to room temperature, then with insoluble solids centrifugation-washing, behind the several separator was put into 60 ℃ of vacuum drying ovens dry 24 hours repeatedly, promptly obtained Comparative Examples two catalyst I r
0.6Ru
0.4O
2
As can beappreciated from fig. 8, prepared catalyst Ir of the present invention
0.6Ru
0.4Mo
0.05O
2.15Monocell performance as anode catalyst is superior to catalyst I r in the Comparative Examples two
0.6Ru
0.4O
2Monocell performance as anode catalyst.
Embodiment 5
With 0.1863g chloro-iridic acid (H
2IrCl
66H
2O), 0.0587g ruthenic chloride (RuCl
32H
2O), 0.1073g ammonium tungstate ((NH
4)
5H
5[H
2(WO
4)
6] H
2O) be dissolved in the 50ml deionized water, wherein the Ir/Ru mol ratio is 3/2.Add 10g potassium nitrate (KNO
3), stir and make its dissolving, adding 0.5M ammoniacal liquor adjusting pH value then is 8.To mix back solution and place 80 ℃ of temperature stirred in water bath evaporates to dryness, place 80 ℃ of dry 12h of baking oven then.With the solid abrasive that obtains, place tube furnace then, rise to 350 ℃ with 10 ℃/minute earlier, rise to 550 ℃ with 5 ℃/minute again, and be incubated 1 hour down at 550 ℃.The adding deionized water dissolved DDGS after thing to be generated was cooled to room temperature, then with insoluble solids centrifugation-washing, behind the several separator was put into 60 ℃ of vacuum drying ovens dry 24 hours repeatedly, promptly obtained catalyst I r of the present invention
0.6Ru
0.4W
0.03O
2.09
As can beappreciated from fig. 9, prepared catalyst Ir of the present invention
0.6Ru
0.4W
0.03O
2.09Monocell performance as anode catalyst is superior to catalyst I r in the Comparative Examples two
0.6Ru
0.4O
2Monocell performance as anode catalyst.
Embodiment 6
With 0.2678g chloro-iridic acid (H
2IrCl
66H
2O), 0.0844g ruthenic chloride (RuCl
32H
2O), 0.231g chromic nitrate (Cr (NO
3)
39H
2O) be dissolved in the 50ml deionized water, wherein the Ir/Ru mol ratio is 3/2.Add 10g potassium nitrate (KNO
3), stir and make its dissolving, adding 0.5M ammoniacal liquor adjusting pH value then is 8.To mix back solution and place 80 ℃ of temperature stirred in water bath evaporates to dryness, place 80 ℃ of dry 12h of baking oven then.With the solid abrasive that obtains, place tube furnace then, rise to 350 ℃ with 10 ℃/minute earlier, rise to 550 ℃ with 5 ℃/minute again, and be incubated 1 hour down at 550 ℃.The adding deionized water dissolved DDGS after thing to be generated was cooled to room temperature, then with insoluble solids centrifugation-washing, behind the several separator was put into 60 ℃ of vacuum drying ovens dry 24 hours repeatedly, promptly obtained catalyst I r of the present invention
0.6Ru
0.4Cr
0.12O
2.36
As can beappreciated from fig. 10, prepared catalyst Ir of the present invention
0.6Ru
0.4Cr
0.12O
2.36Monocell performance as anode catalyst is superior to catalyst I r in the Comparative Examples two
0.6Ru
0.4O
2Monocell performance as anode catalyst.
Claims (9)
1. a catalyst for water electrolysis is characterized in that: said catalyst useful molecules formula Ir
xRu
1-xM
yO
zExpression, 0＜x＜1,0＜y≤0.3,1.5＜z≤2.9 wherein, wherein M is Mo, W, one or more among the Cr.
2. according to the said catalyst of claim 1, it is characterized in that: the ratio that said M accounts for the catalyst gross weight less than 10wt% greater than 0wt%.
3. according to the said catalyst of claim 2, it is characterized in that: said M accounts for the ratio 2～6wt% of catalyst gross weight.
4. according to the said catalyst of claim 2, it is characterized in that: said M accounts for the ratio 2.73～5wt% of catalyst gross weight.
5. said Preparation of catalysts method of claim 1 is characterized in that:
(1) by required metering ratio; The solubility precursor compound of yttrium oxide, ruthenium-oxide and the solubility precursor compound of doped chemical M are dissolved in deionized water; The molar concentration that the precursor compound of above-mentioned yttrium oxide, ruthenium-oxide and M is dissolved in the deionized water is 2～3mol/l; Using alkali to regulate pH value is 7～8, obtains solution A;
(2) in A, add alkali-metal nitrate, under the stirring in 60-80 ℃ of water-bath evaporate to dryness, obtain mixture B;
(3) with mixture B dry 6～24h in 60～80 ℃ of baking ovens, 350～600 ℃ of roasting 0.5～1h obtain pressed powder C in the air;
(4) pressed powder C is spent deionised water and be placed on 60～80 ℃ of oven dry in the vacuum drying oven, obtain catalyst product.
6. according to the said Preparation of catalysts method of claim 5, it is characterized in that: the yttrium oxide precursor compound described in the step (1) is IrCl
3, H
2IrCl
66H
2O; The precursor compound of the ruthenium-oxide described in the step (1) is RuCl
3The precursor compound of doped chemical M described in the step (1) is H
2MoO
42H
2O, ammonium molybdate, ammonium tungstate, chromic nitrate or chromium trioxide; Alkali described in the step (1) is the NaOH aqueous solution, NaHCO
3The aqueous solution or ammoniacal liquor; Alkali-metal nitrate is KNO described in the step (2)
3, NaNO
3Or LiNO
3Alkali-metal nitrate addition described in the step (2) is the corresponding adding 50～75g of preparation 1g catalyst.
The said catalyst of claim 1 in solid polymer electrolyte SPE water electrolysis reaction as the application of anode catalyst.
8. according to the said Application of Catalyst of claim 7, it is characterized in that: the said catalyst of claim 1 is used for the anode-side of solid polymer electrolyte water electrolysis device as anode catalyst.
9. the application of the catalyst in the claim 1 in renewable formula fuel cell (RFC), sensor, electrolysis oxygenerator.
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| CN103170329B (en) * | 2011-12-22 | 2014-12-10 | 中国科学院大连化学物理研究所 | Preparation method of double-effect oxygen electrode catalyst with core-shell structure for fuel cells |
| US20160083857A1 (en) * | 2014-09-18 | 2016-03-24 | Phillips 66 Company | Voltage efficiency of alkaline water electrolysis by using a mixed metal oxide cathode catalyst |
| CN106111130B (en) * | 2016-06-27 | 2018-09-14 | 中国科学院长春应用化学研究所 | A kind of porous superhigh specific surface area IrO2Oxygen-separating catalyst and preparation method thereof |
| CN107630228A (en) * | 2017-09-19 | 2018-01-26 | 中国科学院长春应用化学研究所 | A kind of nano-porous structure oxygen-separating catalyst of surface oxidation iridium enrichment and preparation method thereof |
| CN108043437B (en) * | 2017-11-09 | 2023-09-22 | 国家电网公司 | Preparation method of hollow SiC carrier type Ir-Ru catalyst |
| CN108823589A (en) * | 2018-06-11 | 2018-11-16 | 浙江高成绿能科技有限公司 | A kind of preparation process of solid polymer water electrolysis oxygen-separating catalyst yttrium oxide |
| CN110787810A (en) * | 2019-11-16 | 2020-02-14 | 许昌学院 | Preparation method and application of ruthenium-cobalt binary catalyst |
| KR102317733B1 (en) * | 2019-11-25 | 2021-10-27 | 광주과학기술원 | Catalyst compound, water electrolyser comprising thereof and synthetic method of catalyst compound |
| WO2021108461A1 (en) * | 2019-11-25 | 2021-06-03 | The Regents Of The University Of California | Iridium-based amorphous electrocatalyst and synthesis of same |
| CN111375408B (en) * | 2020-02-15 | 2022-07-08 | 中国工程物理研究院材料研究所 | Preparation method and application of iridium oxide nanoparticle catalyst |
| CN111905724B (en) * | 2020-07-08 | 2023-04-25 | 深圳大学 | Ruthenium oxide catalyst, and preparation method and application thereof |
| CN112725828B (en) * | 2020-12-28 | 2021-11-23 | 宁波中科科创新能源科技有限公司 | IrRu-based multicomponent alloy metal precipitation catalyst and preparation method thereof |
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