CN101884930A - Perovskite-type LaxCa1-xCoO3/Ag compound powder oxygen reduction catalyst and preparation method - Google Patents
Perovskite-type LaxCa1-xCoO3/Ag compound powder oxygen reduction catalyst and preparation method Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000001301 oxygen Substances 0.000 title claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 title abstract 4
- 239000000126 substance Substances 0.000 claims abstract description 15
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 11
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims description 41
- 229910018921 CoO 3 Inorganic materials 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 5
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 17
- 238000000151 deposition Methods 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000008139 complexing agent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229910001961 silver nitrate Inorganic materials 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for preparing a perovskite-type LaxCa1-xCoO3/Ag compound powder oxygen reduction catalyst, which comprises the following steps of: carrying out process treatment of sol-gel, drying, ageing, baking, high-temperature roasting and the like by using calcium nitrate, cobalt nitrate and lanthanum nitrate as raw materials to prepare LaxCa1-xCoO3 powder; carrying out chemical reaction by using silver nitrate as a raw material, using distilled water as a solvent and using ammonia as a complexing agent to prepare a silver-ammonia complex solution; and adding LaxCa1-xCoO3 powder, and depositing an elementary substance Ag on the surface of the perovskite by means of liquid-phase chemical reduction to obtain the perovskite-type LaxCa1-xCoO3/Ag compound powder oxygen reduction catalyst. In the invention, compared with the traditional perovskite-type oxide catalyst, the electrical conductivity of the prepared compound powder catalyst is increased, the catalytic activity is increased, and meanwhile, the cost is greatly lower than that of a pure Ag elementary catalyst. The catalyst can be used for low-temperature alkaline fuel cells or metal-air cells and can be used as a catalyst on a cathode for reducing O2 to be OH<->.
Description
Technical field
The present invention relates to a kind of Ca-Ti ore type La
xCa
1-xCoO
3/ Ag composite granule oxygen reduction catalyst and preparation method thereof.This catalyst is as low-temperature alkali fuel battery negative pole oxygen reduction catalyst, or the metal-air battery cathod catalyst of alkalescence.It is the crucial electrode catalytic materials that influences power of battery density.
Background technology
For high energy low-temperature alkali fuel cell and high-energy metals-air green battery, oxygen electrode (or air electrode) catalyst is one of key factor that improves its performance, perovskite composite oxide is with its efficient, durable and cheap characteristics in adopted catalyst, and receives much concern.Because efficient, environmental protection characteristics that low-temperature fuel cell and metal-air battery are intrinsic are with a wide range of applications.At present, Japan, Europe, the U.S. and domestic how tame colleges and universities and scientific research institution have all carried out the research work of perovskite type composite oxide catalyst aspect.But the electronic conductivity of perofskite type oxide powder is not high, how to improve electrical conductivity and be always one of emphasis that the scientific worker studies.
Summary of the invention
The objective of the invention is at the not high defective of perovskite type composite oxide catalyst electrical conductivity, the La that a kind of catalysis characteristics is better, electrical conductivity is higher is provided
xCa
1-xCoO
3/ Ag composite powder body catalyst and preparation method.
Technical scheme of the present invention is:
La
xCa
1-xCoO
3/ Ag composite powder body catalyst prepares by the following method:
The first step: in molar ratio 0.2～0.8: 1: 1～0.2, take by weighing calcium nitrate Ca (NO
3)
24H
2O, cobalt nitrate Co (NO
3)
26H
2O, lanthanum nitrate
Be dissolved in the distilled water stand-byly, the solution that takes a morsel is adjusted to 0.9～3.0 with nitric acid and ammoniacal liquor with the pH value, adds the citric acid of 1～5%wt, and solution makes colloidal sol 40～95 ℃ of constant temperature hydrolysis then;
Second step: the moisture evaporate to dryness with colloidal sol, obtain pink gel, ageing is 10～72 hours under the room temperature;
The 3rd step: the gel after the ageing is put in the Muffle furnace, begins to be warming up to 500 ℃ from room temperature, be incubated 2～8 hours, the remaining nitrate anion in the gel is decomposed, cooling naturally obtains black powder afterwards;
The 4th goes on foot: black powder is transferred to ground fine ground in the alms bowl, place corundum crucible, 700～900 ℃ of following roastings, make it at high temperature change the perovskite structure phase into electric furnace, be incubated 6～24 hours, make La
xCa
1-xCoO
3Powder;
The 5th step: the AgNO of preparation 1M～5M
3Solution adds ammoniacal liquor in solution, generate precipitation, continues to add ammoniacal liquor precipitation is disappeared, and makes it form silver ammonia complex.Then, be toward silver ammonia complex solution in to add the La that made at 0.90～0.999: 0.10～0.001 by the mass ratio of perovskite oxide and Ag
xCa
1-xCoO
3Powder; Drip the solution of reducing agent hydrazine hydrate (or formaldehyde or sodium potassium tartrate tetrahydrate) again, drip while stirring, addition is 1.2～2 times of reduction silver ion aequum; And temperature constant is between 20～60 ℃, after filtration, clean, the heating evaporate to dryness makes the La that simple substance Ag is deposited on the perofskite type oxide surface
xCa
1-xCoO
3/ Ag composite granule.
The present invention uses the auxiliary sol-gel process of organic acid to prepare La
xCa
1-xCoO
3Perofskite type oxide, then, by the liquid phase chemical reduction method at La
xCa
1-xCoO
3Particle surface deposition simple substance Ag makes La
xCa
1-xCoO
3/ Ag composite powder body catalyst has silver-colored addition minimizing, the more high outstanding advantage of electrical conductivity.Because the concerted catalysis effect of Ag and perovskite oxide, the hydrogen reduction catalytic activity of the catalyst that the present invention obtains is also higher, even more taller than the catalyst activity that just adds silver ion before the roasting.This catalyst can be used in low-temperature alkali fuel cell or the metal-air battery, as on the negative electrode with O
2Be reduced to OH
-Catalyst.This composite powder body catalyst can promote the exploitation of high efficiency oxygen electrode or air electrode, and then promotes the industrialization of above-mentioned novel green battery.
The present invention has prepared the La that catalytic activity is better, electrical conductivity is higher
xCa
1-xCoO
3/ Ag composite granule, and the preparation method is simple, and process is easy to control.
The specific embodiment
Embodiment one:
The first step: 0.6: 1: 0.4 in molar ratio, take by weighing calcium nitrate Ca (NO
3)
24H
2O, cobalt nitrate Co (NO
3)
26H
2O, lanthanum nitrate
Be dissolved in the distilled water stand-byly, the solution that takes a morsel adjusts to 1.8 with nitric acid and ammoniacal liquor with the pH value, adds the citric acid of 2%wt, and solution makes colloidal sol 80 ℃ of constant temperature hydrolysis then;
Second step: the moisture evaporate to dryness with colloidal sol, obtain pink gel, ageing is 48 hours under the room temperature;
The 3rd step: the gel of ageing after 48 hours is put in the Muffle furnace under the above-mentioned room temperature, begins to be warming up to 500 ℃ from room temperature, is incubated 4 hours, and the remaining nitrate anion in the gel is decomposed, and cooling naturally obtains black powder afterwards;
The 4th goes on foot: above-mentioned black powder is transferred to ground fine ground in the alms bowl, place corundum crucible again, 700 ℃ of following roastings, make it at high temperature change the perovskite structure phase into electric furnace, be incubated 24 hours, obtain La
0.4Ca
0.6CoO
3Powder;
The 5th step: the AgNO of preparation 2M
3Solution adds ammoniacal liquor in solution, generate precipitation, continues to add ammoniacal liquor precipitation is disappeared, and makes it form silver ammonia complex, then, is the La that adding had made in the silver ammonia complex solution in 0.98: 0.02 by the mass ratio of perovskite oxide and Ag
0.4Ca
0.6CoO
3Powder; Drip the solution of reducing agent hydrazine hydrate (or formaldehyde or sodium potassium tartrate tetrahydrate) again, drip while stirring, addition is 1.5 times of reduction silver ion aequum; And temperature constant is between 30 ℃, after filtration, clean, the heating evaporate to dryness makes the La that simple substance Ag is deposited on the perofskite type oxide surface
0.4Ca
0.6CoO
3/ Ag composite granule, the deposition of simple substance Ag is controlled at 2%wt.
Behind above-mentioned catalyst fines sample compressing tablet, measure electrical conductivity by bridge method; Simultaneously, utilization powder electrode technology is measured the apparent exchange current density of catalyst powder, adopts three-electrode system in the measurement, and the KOH solution of 6M is electrolyte, feeds pure oxygen in the electrolytic cell continuously.Measurement shows, through the La of above-mentioned liquid phase chemical reduction deposition 2%wt Ag simple substance
0.4Ca
0.6CoO
3The electrical conductivity of/Ag composite powder is 0.85 Ω
-1Cm
-1, apparent exchange current density reaches 0.4171A/m
2
Comparison example: the process at preparation La-Ca-Co-O sol-gel is just added 2%wtAg
+The La of ion
0.4Ca
0.6CoO
3The electrical conductivity of powder is 1.89 * 10
-1Ω
-1Cm
-1, apparent exchange current density is 0.2988A/m
2
So, use method of the present invention, deposit simple substance Ag at La by liquid phase chemical reduction
0.4Ca
0.6CoO
3The composite powder body catalyst of particle surface has better catalysis characteristics.
Embodiment two:
The first step: 0.8: 1: 0.2 in molar ratio, take by weighing calcium nitrate Ca (NO
3)
24H
2O, cobalt nitrate Co (NO
3)
26H
2O, lanthanum nitrate
Be dissolved in the distilled water stand-byly, the solution that takes a morsel adjusts to 2.5 with nitric acid and ammoniacal liquor with the pH value, adds the citric acid of 4%wt, and solution makes colloidal sol 50 ℃ of constant temperature hydrolysis then;
Second step: the moisture evaporate to dryness with colloidal sol, obtain pink gel, ageing is 72 hours under the room temperature;
The 3rd step: the gel of ageing after 72 hours is put in the Muffle furnace under the above-mentioned room temperature, begins to be warming up to 500 ℃ from room temperature, is incubated 8 hours, and the remaining nitrate anion in the gel is decomposed, and cooling naturally obtains black powder afterwards;
The 4th goes on foot: black powder is transferred to ground fine ground in the alms bowl, sample is placed corundum crucible, 800 ℃ of following roastings, make it at high temperature change the perovskite structure phase into electric furnace, be incubated 14 hours, obtain La
0.2Ca
0.8CoO
3Powder;
The 5th step: the AgNO of preparation 1M
3Solution adds ammoniacal liquor in solution, generate precipitation, continues to add ammoniacal liquor precipitation is disappeared, and makes it form silver ammonia complex, then, is the La that adding had made in the silver ammonia complex solution in 0.99: 0.01 by the mass ratio of perovskite oxide and Ag
0.2Ca
0.8CoO
3Powder; Drip the solution of reducing agent hydrazine hydrate (or formaldehyde or sodium potassium tartrate tetrahydrate) again, drip while stirring, addition is 1.2 times of reduction silver ion aequum; And temperature constant is between 60 ℃, after filtration, clean, the heating evaporate to dryness makes the La that simple substance Ag is deposited on the perofskite type oxide surface
0.2Ca
0.8CoO
3/ Ag composite granule, the deposition of simple substance Ag is controlled at 1%wt.
The performance characterization of composite powder such as embodiment one.By the La of present embodiment through liquid phase chemical reduction deposition 1%wt Ag simple substance
0.4Ca
0.6CoO
3The electrical conductivity of/Ag composite powder is 0.26 Ω
-1Cm
-1, apparent exchange current density reaches 0.3012A/m
2La
0.4Ca
0.6CoO
3/Ag
Comparison example: just add 1%wt Ag at sol-gel process
+The La of ion
0.2Ca
0.8CoO
3The electrical conductivity of powder is 4.73 * 10
-2Ω
-1Cm
-1, apparent exchange current density is 0.0600A/m
2
Embodiment three:
The first step: 0.2: 1: 0.8 in molar ratio, take by weighing calcium nitrate Ca (NO
3)
24H
2O, cobalt nitrate Co (NO
3)
26H
2O, lanthanum nitrate
Be dissolved in the distilled water stand-byly, the solution that takes a morsel adjusts to 0.9 with nitric acid and ammoniacal liquor with the pH value, adds the citric acid of 1%wt, and solution makes colloidal sol 95 ℃ of constant temperature hydrolysis then;
Second step: the moisture evaporate to dryness with colloidal sol, obtain pink gel, ageing is 24 hours under the room temperature;
The 3rd step: the gel of ageing after 48 hours is put in the Muffle furnace under the above-mentioned room temperature, begins to be warming up to 500 ℃ from room temperature, is incubated 2 hours, and the remaining nitrate anion in the gel is decomposed, and cooling naturally obtains black powder afterwards;
The 4th goes on foot: black powder is transferred to ground fine ground in the alms bowl, sample is placed corundum crucible, 900 ℃ of following roastings, make it at high temperature change the perovskite structure phase into electric furnace, be incubated 6 hours, obtain La
0.8Ca
0.2CoO
3Powder;
The 5th step: the AgNO of preparation 4M
3Solution adds ammoniacal liquor in solution, generate precipitation, continues to add ammoniacal liquor precipitation is disappeared, and makes it form silver ammonia complex.Then, be toward silver ammonia complex solution in to add the La that made at 0.96: 0.04 by the mass ratio of perovskite oxide and Ag
0.8Ca
0.2CoO
3Powder; Drip the solution of reducing agent hydrazine hydrate (or formaldehyde or sodium potassium tartrate tetrahydrate) again, drip while stirring, addition is 1.9 times of reduction silver ion aequum; And temperature constant is between 45 ℃, after filtration, clean, the heating evaporate to dryness makes the La that simple substance Ag is deposited on the perofskite type oxide surface
0.8Ca
0.2CoO
3/ Ag composite granule, the deposition of simple substance Ag is controlled at 4%wt.
The performance characterization of composite powder such as embodiment one.By the La of present embodiment through liquid phase chemical reduction deposition 4%wt Ag simple substance
0.8Ca
0.2CoO
3The electrical conductivity of/Ag composite powder is 1.06 Ω
-1Cm
-1, apparent exchange current density reaches 0.6032A/m
2
Comparison example: just add 4%wt Ag at sol-gel process
+The La of ion
0.8Ca
0.2CoO
3The electrical conductivity of powder is 4.12 * 10
-1Ω
-1Cm
-1, apparent exchange current density is 0.0509A/m
2
Can find out by embodiment one, two, three, in the colloidal sol preparation process, just add Ag
+Catalyst powder, catalytic activity increases synchronously with the increase of silver amount.And employing La
xCa
1-xCoO
3Powder preparation well after, at the composite granule of liquid phase chemical deposition Ag simple substance, increase with silver content, the exchange current density of electrical conductivity and catalytic reaction all increases synchronously.Therefore, Ag is deposited on La through liquid phase chemical reduction among employing the present invention
xCa
1-xCoO
3Technology on the particle can be brought into play La better
xCa
1-xCoO
3Catalyzing cooperation effect with Ag gets a greater increase catalytic performance.
Claims (2)
1. Ca-Ti ore type La
xCa
1-xCoO
3The preparation method of/Ag composite granule oxygen reduction catalyst is characterized in that carrying out according to the following steps:
The first step: in molar ratio 0.2～0.8: 1: 1～0.2, take by weighing calcium nitrate Ca (NO
3)
24H
2O, cobalt nitrate Co (NO
3)
26H
2O, lanthanum nitrate La (NO
3)
26H
2O is dissolved in the distilled water stand-by, and the solution that takes a morsel is adjusted to 0.9～3.0 with nitric acid and ammoniacal liquor with the pH value, adds the citric acid of 1～5%wt, and solution makes colloidal sol 40～95 ℃ of constant temperature hydrolysis then;
Second step: the moisture evaporate to dryness with colloidal sol, obtain pink gel, ageing is 10～72 hours under the room temperature;
The 3rd step: the gel after the ageing is put in the Muffle furnace, begins to be warming up to 500 ℃ from room temperature, be incubated 2～8 hours, the remaining nitrate anion in the gel is decomposed, cooling naturally obtains black powder afterwards;
The 4th goes on foot: black powder is transferred to ground fine ground in the alms bowl, place corundum crucible, 700～900 ℃ of following roastings, make it at high temperature change the perovskite structure phase into electric furnace, be incubated 6～24 hours, make La
xCa
1-xCoO
3Powder;
The 5th step: the AgNO of preparation 1M～5M
3Solution adds ammoniacal liquor in solution, generate precipitation, continuing to add ammoniacal liquor disappears precipitation, making it form silver ammonia complex, then, is 0.90～0.999: 0.10～0.001 La that adding has made in the silver ammonia complex solution by the mass ratio of perovskite oxide and Ag
xCa
1-xCoO
3Powder; Drip the solution of reducing agent hydrazine hydrate or formaldehyde or sodium potassium tartrate tetrahydrate again, drip while stirring, addition is 1.2～2 times of reduction silver ion aequum; And temperature constant is between 20～60 ℃, after filtration, clean, the heating evaporate to dryness makes the La of simple substance deposition of silver on the perofskite type oxide surface
xCa
1-xCoO
3/ Ag composite granule.
2. press the described Ca-Ti ore type La of claim 1 for one kind
xCa
1-xCoO
3The La of preparation method's preparation of/Ag composite granule oxygen reduction catalyst
xCa
1-xCoO
3/ Ag composite granule oxygen reduction catalyst.
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|---|---|---|---|
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|---|---|---|---|
| CN2010102197266A CN101884930A (en) | 2010-07-07 | 2010-07-07 | Perovskite-type LaxCa1-xCoO3/Ag compound powder oxygen reduction catalyst and preparation method |
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|---|---|
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|---|---|---|---|
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|---|---|---|---|---|
| CN102166517A (en) * | 2011-03-21 | 2011-08-31 | 北京中航长力能源科技有限公司 | Preparation method and application of perovskite type composite oxide catalyst |
| CN102179242A (en) * | 2011-03-23 | 2011-09-14 | 天津大学 | Preparation of non-precious metal nitric oxide storage reduction catalyst LaMnO3/ K/ZrTiO4 and application thereof |
| CN102658152A (en) * | 2012-04-19 | 2012-09-12 | 常州优特科新能源科技有限公司 | Method for preparing oxygen electrode perovskite-type catalyst |
| CN102862954A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production |
| CN103413924B (en) * | 2013-06-17 | 2016-03-30 | 昆明理工大学 | A kind of La 1-xca xcoO 3coated lithium ion battery LiNi 1/3co 1/3mn 1/3o 2positive electrode and preparation method thereof |
| CN106348757A (en) * | 2016-08-25 | 2017-01-25 | 盐城工学院 | La1-xCaxCoO3 and preparation method thereof as well as application in preparation of infrared radiation material and coating material |
| CN111454059A (en) * | 2020-05-20 | 2020-07-28 | 中国科学院重庆绿色智能技术研究院 | Preparation of L axSr1-xCoO3-Method for preparing composite oxide |
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| CN102166517A (en) * | 2011-03-21 | 2011-08-31 | 北京中航长力能源科技有限公司 | Preparation method and application of perovskite type composite oxide catalyst |
| CN102166517B (en) * | 2011-03-21 | 2012-06-27 | 北京中航长力能源科技有限公司 | Preparation method and application of perovskite type composite oxide catalyst |
| CN102179242A (en) * | 2011-03-23 | 2011-09-14 | 天津大学 | Preparation of non-precious metal nitric oxide storage reduction catalyst LaMnO3/ K/ZrTiO4 and application thereof |
| CN102862954A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production |
| CN102862954B (en) * | 2011-07-07 | 2014-10-15 | 中国石油化工股份有限公司 | Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production |
| CN102658152A (en) * | 2012-04-19 | 2012-09-12 | 常州优特科新能源科技有限公司 | Method for preparing oxygen electrode perovskite-type catalyst |
| CN102658152B (en) * | 2012-04-19 | 2014-05-14 | 常州优特科新能源科技有限公司 | Method for preparing oxygen electrode perovskite-type catalyst |
| CN103413924B (en) * | 2013-06-17 | 2016-03-30 | 昆明理工大学 | A kind of La 1-xca xcoO 3coated lithium ion battery LiNi 1/3co 1/3mn 1/3o 2positive electrode and preparation method thereof |
| CN106348757A (en) * | 2016-08-25 | 2017-01-25 | 盐城工学院 | La1-xCaxCoO3 and preparation method thereof as well as application in preparation of infrared radiation material and coating material |
| CN111454059A (en) * | 2020-05-20 | 2020-07-28 | 中国科学院重庆绿色智能技术研究院 | Preparation of L axSr1-xCoO3-Method for preparing composite oxide |
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