CN101733095A - Catalyst for water electrolysis and preparation and application thereof - Google Patents

Catalyst for water electrolysis and preparation and application thereof Download PDF

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CN101733095A
CN101733095A CN200810228708A CN200810228708A CN101733095A CN 101733095 A CN101733095 A CN 101733095A CN 200810228708 A CN200810228708 A CN 200810228708A CN 200810228708 A CN200810228708 A CN 200810228708A CN 101733095 A CN101733095 A CN 101733095A
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anode
water electrolysis
water
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CN101733095B (en
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张华民
程金斌
陈国宝
张益宁
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Dalian Institute of Chemical Physics of CAS
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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

A kind of catalyst for water electrolysis and preparation thereof and application
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.
Figure G2008102287087D0000011
Think RuO with Stucki 2The reason that is corroded is RuO in the OER process 2Be oxidized into the RuO of solubility 4[R.
Figure G2008102287087D0000012
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 by 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 described 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 HydrogenEnergy 32 (2007) 2320], Ir thought in article 0.6Ru 0.4O 2At Ir xRu yTa zO 2In have best catalytic activity, the adding of Ta is not significantly increased 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 (as 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.
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 (as 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 achieving the above object, the technical solution used in the present invention is:
A kind of catalyst for water electrolysis, 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.
The ratio that described 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, regulating pH value with alkali 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 may 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 (as isopropyl alcohol) are mixed into the slurry of homogeneous through sonic oscillation, by the method for spraying, printing, curtain coating slurry is deposited to uniformly the both sides of Nafion1035 film then, treat to make 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 of the present invention, and loading is 0.5～3mg/cm 2At cathode side, use Pt catalyst (as 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 of the present invention is compound (homogeneous phase), and doping component content is low; And the described catalyst of other related invention mostly 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 of the present invention to be used for SPE apparatus for electrolyzing anode result of use be better than the not mixing catalyst of element of the present 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 by 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 as follows: with the Nafion solution blending of 1ml isopropyl alcohol, 5mg catalyst and 50 μ L 5wt%, 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 illustrates 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 illustrates 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
Now adopt following examples and Comparative Examples explanation the present invention, but the present invention is not subjected to the restriction of following examples and Comparative Examples.
Embodiment 1
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 by 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 be seen from Figure 1, catalyst of the present invention and Comparative Examples one catalyst are the rutile phase structure, calculate the catalyst crystallite particle size by 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 may 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 be seen from Figure 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 be seen from Figure 3, prepared catalyst Ir of the present invention 0.4Ru 0.6Mo 0.05O 2.15Monocell performance as anode catalyst is better than 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 be seen from Figure 4, catalyst of the present invention and Comparative Examples one catalyst are the rutile phase structure, calculate the catalyst crystallite particle size by 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 be seen from Figure 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 be seen from Figure 6, prepared catalyst Ir of the present invention 0.4Ru 0.6W 0.03O 2.09Monocell performance as anode catalyst is better than 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 be seen from Figure 7, prepared catalyst Ir of the present invention 0.4Ru 0.6Cr 0.12O 2.36Monocell performance as anode catalyst is better than 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 be seen from Figure 8, prepared catalyst Ir of the present invention 0.6Ru 0.4Mo 0.05O 2.15Monocell performance as anode catalyst is better than 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 be seen from Figure 9, prepared catalyst Ir of the present invention 0.6Ru 0.4W 0.03O 2.09Monocell performance as anode catalyst is better than 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 be seen from Figure 10, prepared catalyst Ir of the present invention 0.6Ru 0.4Cr 0.12O 2.36Monocell performance as anode catalyst is better than 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: described 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 described catalyst of claim 1, it is characterized in that: the ratio that described M accounts for the catalyst gross weight less than 10wt% greater than 0wt%.
3. according to the described catalyst of claim 2, it is characterized in that: described M accounts for the ratio 2～6wt% of catalyst gross weight.
4. according to the described catalyst of claim 2, it is characterized in that: described M accounts for the ratio 2.73～5wt% of catalyst gross weight.
5. described 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 of the precursor compound of above-mentioned yttrium oxide, ruthenium-oxide and M in deionized water is 2～3mol/l, regulating pH value with alkali 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 described Preparation of catalysts method of claim 5, it is characterized in that: the yttrium oxide precursor compound described in the step (1) can be IrCl 3, H 2IrCl 66H 2O; The precursor compound of the ruthenium-oxide described in the step (1) can be RuCl 3The precursor compound of doped chemical M described in the step (1) can be H 2MoO 42H 2O, ammonium molybdate, ammonium tungstate, chromic nitrate, 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 described catalyst of claim 1 in solid polymer electrolyte SPE water electrolysis reaction as the application of anode catalyst.
8. according to the described Application of Catalyst of claim 7, it is characterized in that: the described catalyst of claim 1 is used for the anode-side of solid polymer electrolyte water electrolysis device as anode catalyst.
9. the application of each catalyst in renewable formula fuel cell (RFC), sensor, electrolysis oxygenerator in the claim 1.
CN2008102287087A 2008-11-12 2008-11-12 Catalyst for water electrolysis and preparation and application thereof Expired - Fee Related CN101733095B (en)

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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
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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
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CN110787810A (en) * 2019-11-16 2020-02-14 许昌学院 Preparation method and application of ruthenium-cobalt binary catalyst
KR20210063909A (en) * 2019-11-25 2021-06-02 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
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