Method for preparing perovskite oxide-based catalyst particles
View Patent ↗A high-surface area fine particle dispersal of LaMnO 3 or a promoted derivation of LaMnO 3 may be prepared by the citrate method. The amount of citric acid used to complex the constituent metal cations into citrate complexed mixed metal compounds may range from about 40 mol % to about 100 mol % in excess of stoichiometry.
1. A method comprising:
dissolving precursor constituent metal salts, which comprise salts of Lanthanum and manganese, and an amount of citric acid into water to form an aqueous liquid medium, the precursor constituent metal salts providing dissolved constituent metal cations that react with citric acid to form citrate complexed mixed metal compounds, the amount of citric acid included in the aqueous liquid medium ranging from about 40 mol % to about 100 mol % in excess of that needed to stoichiometrically complex with the dissolved constituent metal cations;
removing water from the aqueous liquid medium to concentrate the citrate complexed mixed metal compounds into an amorphous gel;
converting the citrate complexed mixed metal compounds into perovskite oxide particles having a crystal structure represented by the general formula La 1-x A1 x MnO 3 , wherein A1 is a promoter metal cation and x ranges from about 0 to about 0.5.
2. The method according to claim 1 , wherein the amount of citric acid included in the aqueous liquid medium ranges from about 50 mol % to about 70 mol % in excess of that needed to stoichiometrically complex with the dissolved constituent metal cations.
3. The method according to claim 1 , wherein the amount of citric acid included in the aqueous liquid medium is about 60 mol % in excess of that needed to stoichiometrically complex with the dissolved constituent metal cations.
4. The method according to claim 1 , wherein the salts of lanthanum and manganese are lanthanum nitrate and manganese nitrate, respectively.
5. The method according to claim 1 , wherein the precursor constituent metal salts consist of salts of lanthanum and manganese, and wherein the crystal structure of the perovskite oxide particles is represented by the formula LaMnO 3 .
6. The method according to claim 1 , wherein the precursor constituent metal salts further comprise a salt of strontium so that the promoter metal cation is strontium and the crystal structure of the perovskite oxide particles is represented by the formula La 1-x Sr x MnO 3 with x ranging from about 0.01 to about 0.50.
7. The method according to claim 6 , wherein the salt of strontium is strontium nitrate.
8. The method according to claim 1 , wherein the precursor constituent metal salts further comprise a salt of cerium so that the promoter metal cation is cerium and the crystal structure of the perovskite oxide particles is represented by the formula La 1-x Ce x MnO 3 with x ranging from about 0.01 to about 0.50.
9. The method according to claim 8 , wherein the salt of cerium is cerium nitrate.
10. The method according to claim 1 , wherein removing the water from the aqueous liquid medium comprises heating the aqueous liquid medium to a temperature between about 60° C. and 150° C. to evaporate the water.
11. The method according to claim 1 , wherein converting the citrate complexed mixed metal compounds into perovskite oxide particles comprises:
thermally decomposing the amorphous gel in air to evolve nitrogen oxide gases and citrate-derived gases, the thermal decomposition of the amorphous gel forming mixed metal oxide particles; and
calcining the mixed metal oxide particles in air to reconfigure the mixed metal oxide particles into the perovskite oxide particles.
12. The method according to claim 11 , wherein thermally decomposing the amorphous gel comprises heating the amorphous gel in air up to a temperature between about 200° C. and about 300° C. and maintaining that temperature for a period of about five minutes to about 2 hours.
13. The method according to claim 11 , wherein calcining the mixed metal oxide particles comprises heating the mixed metal oxide particles in air at a temperature between about 675° C. and about 1100° C. about 2 hours to about 6 hours.
14. The method according to claim 1 , wherein converting the citrate complexed mixed metal compounds into perovskite oxide particles comprises:
heating the amorphous gel in air up to a temperature between about 200° C. to about 300° C. and maintaining that temperature for a period of about five minutes to about 2 hours to form mixed metal oxide particles primarily defined by a crystal structure dissimilar from the perovskite oxide particles; and
heating the mixed metal oxide particles in air at a temperature between about 675° C. and about 1100° C. for about 2 hours to about 6 hours.
15. A method for preparing perovskite oxide particles, the method comprising:
dissolving an amount of citric acid and nitrate salts of lanthanum, manganese, and a promoter metal into water to form an aqueous liquid medium, the nitrate salts providing dissolved cations of lanthanum, manganese, and the promoter metal that react with citric acid to form citrate complexed mixed metal compounds, the amount of citric acid included in the aqueous liquid medium ranging from about 40 mol % to about 100 mol % in excess of that needed to stoichiometrically complex with the dissolved cations of lanthanum, manganese, and the promoter metal;
heating the aqueous liquid medium to a temperature between about 60° C. and 150° C. to evaporate the water and concentrate the citrate complexed mixed metal compounds into an amorphous gel;
heating the amorphous gel in air up to a temperature between about 200° C. and about 300° C. and maintaining that temperature for a period of about five minutes to about 2 hours to form mixed metal oxide particles primarily defined by a crystal structure dissimilar from perovskite oxide particles; and
heating the mixed metal oxide particles in air at a temperature between about 675° C. and about 1100° C. for about 2 hours to about 6 hours to convert the mixed metal oxide particles into perovskite oxide particles having a crystal structure represented by the general formula La 1-x A1 x MnO 3 , wherein A1 is the promoter metal cation and x ranges from about 0.01 to about 0.5.
16. The method according to claim 15 , wherein the promoter metal cation is a strontium cation and the perovskite oxide particles have a crystal structure represented by the general formula La 1-X Sr X MnO 3 .
17. The method according to claim 15 , wherein the promoter metal cation is a cerium cation and the perovskite oxide particles have a crystal structure represented by the general formula La 1-X Ce X MnO 3 .
18. The method according to claim 15 , wherein the amount of citric acid included in the aqueous liquid medium ranges from about 50 mol % to about 70 mol % in excess of that needed to stoichiometrically complex with the dissolved cations of lanthanum, manganese, and the promoter metal.
19. The method according to claim 15 , wherein the amount of citric acid included in the aqueous liquid medium is about 60 mol % in excess of that needed to stoichiometrically complex with the dissolved cations of lanthanum, manganese, and the promoter metal.