High porosity cerium and zirconium containing oxide

Abstract

This disclosure generally relates to an oxide composition basically composed of cerium and zirconium that has exceptional and stable porosity, surface area and lattice oxygen mobility. The oxide composition can contain one or more other rare earth oxides other than cerium oxide. For example, some compositions can contain one or more of lanthanum oxide, yttrium oxide and neodymium oxide. The oxide composition can be useful as a catalyst, catalyst support, sensor applications and combinations thereof.

Claims

1. A composition comprising zirconium oxide, cerium oxide and optionally one or more other rare earth oxides other than cerium oxide, wherein the composition has a hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for 10 hours of from about 0.5 to about 1.1 molar ratio of H.sub.2 consumption/CeO.sub.2, and wherein one or more of the following are true: (i) wherein the composition has a total pore volume of about 0.7 to about 3.5 cc/g; and (ii) wherein the composition has one or more of a BET and apparent surface area selected from the group consisting of from about 1.0 to about 6.0 m.sup.2/g after calcinations at 1200 degrees Celsius for a period of 10 hours or more in an oxidizing environment, from about 20 m.sup.2/g to about 30 m.sup.2/g after calcination at 1100 degrees Celsius for a period of 10 hours in an oxidizing environment, from about 45 m.sup.2/g to about 70 m.sup.2/g after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment, and combinations thereof.

2. The composition of claim 1, wherein (i) is true.

3. The composition of claim 2, wherein the total pore volume is about 0.7 cc/g, and wherein the hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for 10 hours is about 0.5 molar ratio of H.sub.2 consumption/CeO.sub.2.

4. The composition of claim 2, wherein the total pore volume is about 3.20 cc/g, and wherein the hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment is about 0.99 molar ratio of H.sub.2 consumption/CeO.sub.2.

5. The composition of claim 2, wherein the total pore volume is about 0.7 cc/g, and wherein the hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment is about 0.99 molar ratio of H.sub.2 consumption/CeO.sub.2.

6. The composition of claim 2, wherein the total pore volume is about 3.20 cc/g, and wherein the hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for 10 hours is about 0.5 molar ratio of H.sub.2 consumption/CeO.sub.2.

7. The composition of claim 1, wherein (i) and (iii) are true.

8. The composition of claim 7, wherein the total pore volume is about 0.7 cc/g, and wherein the one or more of a BET and apparent surface area is about 20 m.sup.2/g after calcination at 1100 degrees Celsius for a period of 10 hours in an oxidizing environment.

9. The composition of claim 7, wherein the total pore volume is about 3.20 cc/g, and wherein the one or more of a BET and apparent surface area is about 30 m.sup.2/g after calcination at 1100 degrees Celsius for a period of 10 hours in an oxidizing environment.

10. The composition of claim 7, wherein the total pore volume is about 0.7 cc/g, and wherein the one or more of a BET and apparent surface area is about 45 m.sup.2/g after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment.

11. The composition of claim 7, wherein the total pore volume is about 3.20 cc/g, and wherein the one or more of a BET and apparent surface area is about 70 m.sup.2/g after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment.

12. The composition of claim 1, wherein (ii) is true.

13. The composition of claim 12, wherein the hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for 10 hours is about 0.5 molar ratio of H.sub.2 consumption/CeO.sub.2, and wherein the one or more of a BET and apparent surface area is about 20 m.sup.2/g after calcination at 1100 degrees Celsius for a period of 10 hours in an oxidizing environment.

14. The composition of claim 12, wherein the hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment is about 0.99 molar ratio of H.sub.2 consumption/CeO.sub.2, and wherein the one or more of a BET and apparent surface area is about 30 m.sup.2/g after calcination at 1100 degrees Celsius for a period of 10 hours in an oxidizing environment.

15. The composition of claim 12, wherein the hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment is about 0.99 molar ratio of H.sub.2 consumption/CeO.sub.2, and wherein the one or more of a BET and apparent surface area is about 45 m.sup.2/g after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment.

16. The composition of claim 12, wherein the hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for 10 hours is about 0.5 molar ratio of H.sub.2 consumption/CeO.sub.2, and wherein the one or more of a BET and apparent surface area is about 70 m.sup.2/g after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment.

17. The composition of claim 1, wherein the zirconium oxide comprises from about 1 to about 99 wt % of the composition, wherein the cerium oxide comprises from about 1 to about 99 wt % of composition, and wherein the one or more rare earth oxides other than cerium oxide comprise from about 0.1 to about 30 wt % of the composition.

18. The composition of claim 1, wherein the zirconium oxide comprises from about 60 wt % to about 85 wt % of the composition, wherein the cerium oxide comprises from about 5 wt % to about 30 wt % of the composition.

19. The composition of claim 1, wherein the composition comprises from about 5 wt % to about 20 wt % of the one or more rare earth oxides other than cerium oxide.

20. The composition of claim 1, wherein the composition comprises from about 1.5 wt % to about 6 wt % lanthanum oxide.

21. A composition comprising zirconium oxide, cerium oxide and optionally one or more other rare earth oxides other than cerium oxide, wherein the composition has a hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for 10 hours of from about 0.54 to about 0.99 molar ratio of H.sub.2 consumption/CeO.sub.2, and wherein one or more of the following are true: (i) wherein the composition has a total pore volume of about 0.65 to about 3.20 cc/g; and (ii) wherein the composition has one or more of a BET and apparent surface area selected from the group consisting of from about 1.9 to about 5.2 m.sup.2/g after calcinations at 1200 degrees Celsius for a period of 10 hours or more in an oxidizing environment, from about 24 m.sup.2/g to about 29 m.sup.2/g after calcination at 1100 degrees Celsius for a period of 10 hours in an oxidizing environment, from about 50 m.sup.2/g to about 65 m.sup.2/g after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment, and combinations thereof.

22. The composition of claim 21, wherein (i) is true.

23. The composition of claim 21, wherein (ii) is true.

24. The composition of claim 21, wherein (i) and (ii) are true.

25. The composition of claim 21, wherein the zirconium oxide comprises from about 1 to about 99 wt % of the composition, wherein the cerium oxide comprises from about 1 to about 99 wt % of composition, and wherein the one or more rare earth oxides other than cerium oxide comprise from about 0.1 to about 30 wt % of the composition.

26. The composition of claim 21, wherein the zirconium oxide comprises from about 60 wt % to about 85 wt % of the composition, wherein the cerium oxide comprises from about 5 wt % to about 30 wt % of the composition.

27. The composition of claim 21, wherein the composition comprises from about 5 wt % to about 20 wt % of the one or more rare earth oxides other than cerium oxide.

28. The composition of claim 21, wherein the composition comprises from about 1.5 wt % to about 6 wt % lanthanum oxide.

29. A composition comprising zirconium oxide, cerium oxide and optionally one or more other rare earth oxides other than cerium oxide, wherein the zirconium oxide comprises from about 60 wt % to about 85 wt % of the composition, wherein the cerium oxide comprises from about 5 wt % to about 30 wt % of the composition, wherein the one or more other rare earth oxides other than the cerium oxide or yttrium comprise from about 0.1 to about 30 wt % of the composition, wherein the composition has a hydrogen thermal program reduction uptake after calcination at 1000 degrees Celsius for 10 hours of about 0.5 to about 1.1 molar ratio of H.sub.2 consumption/CeO.sub.2, and wherein one or more of the following are true: (i) wherein the composition has a total pore volume of from about 0.7 to about 3.5 cc/g; and (ii) wherein the composition has one or more of a BET and apparent surface area selected from the group consisting of from about 1.0 to about 6.0 m.sup.2/g after calcinations at 1200 degrees Celsius for a period of 10 hours or more in an oxidizing environment, from about 20 m.sup.2/g to about 30 m.sup.2/g after calcination at 1100 degrees Celsius for a period of 10 hours in an oxidizing environment, from about 45 m.sup.2/g to about 70 m.sup.2/g after calcination at 1000 degrees Celsius for a period of 10 hours in an oxidizing environment, and combinations thereof.

30. The composition of claim 29, wherein (i) and (ii) are true.

Description

DETAILED DESCRIPTION OF FIGURES

(1) The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the disclosure and together with the general description of the disclosure given above and the detailed description given below, serve to explain the principles of the disclosure.

(2) FIG. 1 shows the shows the H.sub.2 thermal programmed reduction components for compositions according to some embodiments of the present disclosure; and

(3) FIG. 2 shows the cumulative and differential pore volume distribution according to some embodiments of present disclosure.

DETAILED DESCRIPTION

(4) The present disclosure describes compositions that have properties that address the above mentioned needs. It is therefore the objective of the present disclosure to provide oxides based on cerium and zirconium that have large and thermally stable surface area, high and thermally stable porosity, large pore openings, high bulk oxygen mobility, that is reversibly reduced and oxidized and to provide a method for the synthesis of such oxides. According to the some embodiments of the disclosure the compositions can be in the form of particles that have a surface area that can be about 50 m.sup.2/g or more after calcination in an oxidizing environment at about 1000 degrees Celsius for about 10 hours. In some embodiments the particles can have a surface area of 24 m.sup.2/g or more after calcination at about 1100 degrees Celsius for about 10 hours in an oxidizing environment.

(5) In accordance with some embodiments of the disclosure, the compositions can comprise oxides. The oxides can be in the form of particles. Moreover, the compositions can have a pore volume of about 1.33 cc/g or more. In some embodiments, the compositions can have a pore volume of about 0.65 cc/g or more after calcination at about 1100 degrees Celsius for about 10 hours in an oxidizing environment.

(6) In accordance with some embodiments of the disclosure, the oxides can be in the form of particles. In some embodiments, the particles can have pore openings. In some embodiments, the pore openings can be from about 130 to about 1000 . In some embodiments, the pore openings can be from about 200 to about 2 m after calcination at about 1100 degrees Celsius for about 10 hours in an oxidizing environment. Typically, the pore openings can have a bi-modal distribution. The first mode can have a median value from about 100 to about 1000 . The second mode can be rather wide and can have a median value from about 1.2 m to about 2.5 m. More typically, the pore openings can a have a median value from 200 to 1 m after calcination at about 1100 degrees Celsius for about 10 hours in an oxidizing environment.

(7) In accordance with some embodiments of the disclosure, the oxides can be in form particles that can contain cerium (IV) oxide. Moreover, the cerium (IV) oxide can have a consumption ratio of H.sub.2/CeO.sub.2 of at about 0.5 or more as measured by a Temperature Programmed Reduction (TPR).

(8) In accordance with some embodiments of the disclosure, the oxides can be in form particles that can have a (H.sub.2) thermal programmed reduction component at a temperature of less than about 400 degrees Celsius. Moreover, the oxides can have a hydrogen (H.sub.2) thermal program reduction component value at a temperature greater than about 400 degrees Celsius.

(9) In accordance with some embodiments of the disclosure is a process for making the composition. Typically, the composition can comprise two or more metal oxides. The process can include a step of obtaining a precipitate by combining the water soluble salts the two or more metals with a base under moderate agitation. The water soluble salts the two or more metals can be any form of the two or more metal salts. Typically, each of the two or more metal salts has a water solubility of more than about 2 g/L. More typically, each of the two or more metal salts have a water solubility of more than about 5 g/L, or even more typically a water solubility of more than about 10 g/L. Even more, typically two or more metal salts comprise nitrates. The process can include a step of washing the obtained precipitate. Furthermore, the process can include a step of dispersing the precipitate in an alcoholic solution to form an alcoholic dispersion. In some embodiments, the process can include charging the alcoholic dispersion to a reactor. Moreover, the process can include a step of raising one or both of the temperature and pressure of the alcoholic dispersion contained within the reactor. Typically, the alcoholic dispersion is raised to a temperature of about 150 C. or more and raised to pressure of about 1 bar or more. Some embodiments of the process include a step of reducing the pressure to atmospheric pressure whilst maintaining the temperature. Some embodiments of the process can include a step of reducing the temperature. Moreover, the process can include a step of recovering a fresh composition. In some embodiments, the process can include a step of calcining the fresh composition. Typically, the fresh composition can be calcined at a temperature of about 300 degrees Celsius or more. More typically, the fresh composition can be calcined at a temperatures of about 300 degrees Celsius or more under one of an oxidizing atmosphere, a reducing atmosphere, an inert atmosphere, or a successive combination of these atmospheres.

(10) The nature and objects of the disclosure are further illustrated by the following example, which is provided for illustrative purposes only and not to limit the disclosure as defined by the claims. The following examples are provided to illustrate certain aspects, embodiments, and configurations of the disclosure and are not to be construed as limitations on the disclosure, as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.

Example 1: 60 wt % ZrO.SUB.2.; 30 wt % CeO.SUB.2.; 6 wt % La.SUB.2.O.SUB.3.; 4 wt % Y.SUB.2.O.SUB.3

(11) A mixed oxide with the composition of oxide equivalent to about 60 wt % ZrO.sub.2, about 30 wt % CeO.sub.2, about 6 wt % La.sub.2O.sub.3, and about 4 wt % Y.sub.2O.sub.3 was synthesized by the following method. Solutions of zirconyl nitrate, cerium (III) nitrate, lanthanum nitrate and yttrium nitrate were combined in appropriate ratios to achieve the targeted elemental compositions of zirconium, cerium, lanthanum and yttrium. Distilled deionized water was then added to achieve a total oxide-based relative concentration of the metals of about 100 grams/liter. Following this adjustment, about 10 ml of hydrogen peroxide (H.sub.2O.sub.2, about 32 wt %) was added to the solution. This solution was then added slowly to a continuously stirred solution of ammonia water (about 1000 ml of about 4.5 molar NH.sub.4OH). The reaction temperature was kept at about 25 degrees Celsius. The resultant precipitate was then filtered and thoroughly washed with distilled de-ionized water at 55 degrees Celsius. The filtered solids were then washed with about 1200 ml of ethanol (about 99%). Following this last step, the solids were filtered and dispersed in ethanol (about 99%) to a total volume of about 675 ml in a stirred Parr reactor model number 4530. The reactor containing the resultant slurry was then fully purged with argon. Following this purge step, the reactor was pressurized with argon to about 10 bar. Subsequently, the reactor was heated until the autogeneously generated pressure reached about 25 bar (at a temperature of about 150 degrees Celsius) at which time, the reactor pressure was lowered by venting and was maintained from about 7 to about 10 bar by venting whilst heating continued to a temperature of about 150 degrees Celsius. At that time, the reactor pressure was lowered by venting to about 1 bar and heating was maintained at a temperature of about 150 degrees Celsius until all the ethanol was substantially eliminated from the material and reactor. The reactor was then cooled to room temperature and the resultant powder material was calcined at about 950 degrees Celsius in air for about 5 hours. The resultant material is defined as material in the fresh state. The fresh material was then further calcined at one of about 1000, about 1100, or about 1200 degrees Celsius, respectively (see Table) for 10 hrs in air for testing (defined as the aging conditions).

Example 2: 60 wt % ZrO.SUB.2.; 30 wt % CeO.SUB.2.; 6 wt % La.SUB.2.O.SUB.3.; 4 wt % Y.SUB.2.O.SUB.3

(12) A mixed oxide with the composition of oxide equivalent of about 60 wt % ZrO.sub.2, about 30 wt % CeO.sub.2, about 6 wt % La.sub.2O.sub.3, and about 4 wt % Y.sub.2O.sub.3 was synthesized by the following method. Solutions of zirconyl nitrate, cerium(III) nitrate, lanthanum nitrate and yttrium nitrate were combined in appropriate ratios to achieve the targeted elemental compositions of zirconium, cerium, lanthanum and yttrium. Distilled deionized water was then added to achieve a total oxide-based relative concentration of the metals of about 100 grams/liter. Following this adjustment, about 10 ml of hydrogen peroxide (H.sub.2O.sub.2, about 32 wt %) was added to the solution. This solution was then added slowly to a continuously stirred solution of ammonia water (about 1000 ml of about 4.5 molar NH.sub.4OH). The reaction temperature was kept at about 25 degrees Celsius. The resultant precipitate was then filtered and thoroughly washed with distilled de-ionized water at about 55 degrees Celsius. The filtered solids were then washed with about 1200 ml of ethanol (about 99%). Following this last step, the solids were filtered and dispersed in ethanol (about 99%) to a total volume of about 675 ml in a stirred Parr reactor model number 4530. The reactor containing the resultant slurry was then fully purged with argon. Following this purge step, the reactor was pressurized with argon to about 10 bar. Subsequently, the reactor was heated until the autogeneously generated pressure reached a maximum pressure of about 30 bar (at about 180 degrees Celsius), more specifically at a pressure of about 20 to about 25 bar (at about 180 degrees Celsius) at which time, the reactor pressure was lowered by venting and was maintained at a pressure of about 17 to about 25 bar whilst heating continued to maintain a temperature of about 180 degrees C. At that time, the reactor was vented to 1 bar and heating continued and was maintained at a temperature of 180 degrees Celsius until all the ethanol was substantially eliminated from the material and reactor. The reactor was then cooled to room temperature and the resultant powder material was calcined at about 950 degrees Celsius in air for about 5 hours. The resultant material is defined as material in the fresh state. The fresh material was then further calcined at one of about 1000, about 1100, and about 1200 degrees Celsius, respectively for about 10 hours in air, see Table, for testing (defined as the aging conditions).

Example 3: 60 wt % ZrO.SUB.2.; 30 wt % CeO.SUB.2.; 6 wt % La.SUB.2.O.SUB.3.; 4 wt % Y.SUB.2.O.SUB.3

(13) A mixed oxide with the composition of oxide equivalent of about 60 wt % ZrO.sub.2, about 30 wt % CeO.sub.2, about 6 wt % La.sub.2O.sub.3, and about 4 wt % Y.sub.2O.sub.3 was synthesized by the following method. Solutions of zirconyl nitrate, cerium(III) nitrate, lanthanum nitrate and yttrium nitrate were combined in appropriate ratios to achieve the targeted elemental compositions of zirconium, cerium, lanthanum and yttrium. Distilled deionized water was then added to achieve a total oxide-based relative concentration of the metals of about 100 grams/liter. Following this adjustment, about 10 ml of hydrogen peroxide (H.sub.2O.sub.2, about 32 wt %) was added to the solution. This solution was then added slowly to a continuously stirred solution of ammonia water (about 1000 ml of about 4.5 molar NH.sub.4O.sub.4). The reaction temperature was kept at about 25 degrees Celsius. The resultant precipitate was then filtered and thoroughly washed with distilled de-ionized water at about 55 degrees Celsius. The filtered solids were then washed with about 1200 ml of ethanol (about 99%). Following this last step, the solids were filtered and dispersed in ethanol (about 99%) to a total volume of about 675 ml in a stirred Parr reactor model number 4530. The reactor containing the resultant slurry was then fully purged with argon. Following this purge step, the reactor was pressurized with argon to about 10 bar. Subsequently, the reactor was heated until the autogeneously generated pressure reached about a maximum pressure of about 50 bar (at about 200 degrees Celsius), more specifically at pressure from about 40 to about 50 bar (at about 200 degrees Celsius at which time the reactor pressure was lowered by venting and was maintained at a pressure from about 25 to about 35 bar by venting whilst heating continued at a temperature of about 200 degrees Celsius. At that time, the reactor was vented to about 1 bar and heating continued and the temperature was maintained at about 200 degrees Celsius until all the ethanol was substantially eliminated from the material and reactor. The reactor was then cooled to room temperature and the resultant powder material was calcined at about 950 degrees Celsius in air for about 5 hours. The resultant material is defined as material in the fresh state. The fresh material was then further calcined at one of about 1000, about 1100, and about 1200 degrees Celsius, respectively, for about 10 hours (see Table) in air for testing (defined as the aging conditions).

Example 4: 72.2 wt % ZrO.SUB.2.; 20.8 wt % CeO.SUB.2.; 1.7 wt % La.SUB.2.O.SUB.3.; 5.3 wt % Nd.SUB.2.O.SUB.3

(14) A mixed oxide with the composition of oxide equivalent of about 72.2 wt % ZrO.sub.2, about 20.8 wt % CeO.sub.2, about 1.7 wt % La.sub.2O.sub.3, and about 5.3 wt % Nd.sub.2O.sub.3 was synthesized by the following method. Solutions of zirconyl nitrate, cerium(III) nitrate, lanthanum nitrate and yttrium nitrate were combined in appropriate ratios to achieve the targeted elemental compositions of zirconium, cerium, lanthanum and neodymium. Distilled deionized water was then added to achieve a total oxide-based relative concentration of the metals of about 100 grams/liter. Following this adjustment, about 7 ml of hydrogen peroxide (H.sub.2O.sub.2, about 32 wt %) was added to the solution. This solution was then added slowly to a continuously stirred solution of ammonia water (about 1000 ml of about 4.5 molar NH.sub.4OH). The reaction temperature was kept at a temperature of about 25 degrees Celsius. The resultant precipitate was then filtered and thoroughly washed with distilled de-ionized water at a temperature of about 55 degrees Celsius. The filtered solids were then washed with about 1200 ml of ethanol (about 99%). Following this last step, the solids were filtered and dispersed in ethanol (about 99%) to a total volume of about 675 ml in a stirred Parr reactor model number 4530. The reactor containing the resultant slurry was then fully purged with argon. Following this purge step, the reactor was pressurized with argon to about 10 bar. Subsequently, the reactor was heated until the autogeneously generated pressure reached about 140 bar at which time, the reactor pressure was maintained at a pressure from about 130 to about 140 bar by venting whilst heating continued to a temperature of about 300 degrees Celsius. At that time, the reactor was vented to about 1 bar and heating continued until all the ethanol was eliminated from the material and reactor. The reactor was then cooled to room temperature and the resultant powder material was calcined at a temperature of about 950 degrees Celsius in air for about 5 hours. The resultant material is defined as material in the fresh state. The fresh material was then further calcined at one of about 1000, about 1100, and about 1200 degrees Celsius, respectively, for about 10 hrs in air (see Table) for testing (defined as the aging conditions).

Example 5: 60 wt % ZrO.SUB.2.; 30 wt % CeO.SUB.2.; 6 wt % La.SUB.2.O.SUB.3.; 4 wt % Y.SUB.2.O.SUB.3

(15) A mixed oxide with the composition of oxide equivalent of about 60 wt % ZrO.sub.2, 30 wt % CeO.sub.2, 6 wt % La.sub.2O.sub.3, and about 4 wt % Y.sub.2O.sub.3 was synthesized by the same method as described in Example 4. The evaluation results are given in the Table.

Example 6: 84 wt % ZrO.SUB.2.; 5 wt % CeO.SUB.2.; 2.5 wt % La.SUB.2.O.SUB.3.; 8.5 wt % Nd.SUB.2.O.SUB.3

(16) A mixed oxide with the composition of oxide equivalent of about 84 wt % ZrO.sub.2, about 5 wt % CeO.sub.2, about 2.5 wt % La.sub.2O.sub.3, and about 8.5 wt % Nd.sub.2O.sub.3 was synthesized by the same method as described in Example 4. The evaluation results are given in the Table.

Example 7: 40 wt % ZrO.SUB.2.; 50 wt % CeO.SUB.2.; 5 wt % La.SUB.2.O.SUB.3.; 5 wt % Y.SUB.2.O.SUB.3

(17) A mixed oxide with the composition of oxide equivalent of about 40% ZrO.sub.2, about 50 wt % CeO.sub.2, about 5 wt % La.sub.2O.sub.3, and about 5 wt % Y.sub.2O.sub.3 was synthesized by the same method as described in Example 4. The evaluation results are given in the Table.

Example 8: 60 wt % ZrO.SUB.2.; 30 wt % CeO.SUB.2.; 6 wt % La.SUB.2.O.SUB.3.; 4 wt % Y.SUB.2.O.SUB.3

(18) A mixed oxide with the composition of oxide equivalent of about 60 wt % ZrO.sub.2, about 30 wt % CeO.sub.2, about 6 wt % La.sub.2O.sub.3, and about 4 wt % Y.sub.2O.sub.3 was synthesized by the following method. Solutions of zirconyl nitrate, cerium(III) nitrate, lanthanum nitrate and yttrium nitrate were combined in appropriate ratios to achieve the targeted elemental compositions of zirconium, cerium, lanthanum and yttrium. Distilled deionized water was then added to achieve a total oxide-based relative concentration of the metals of about 100 grams/liter. Following this adjustment, about 10 ml of hydrogen peroxide (H.sub.2O.sub.2, about 32 wt %) was added to the solution. This solution was then added slowly to a continuously stirred solution of ammonia water (about 1000 ml of about 4.5 molar NH.sub.4OH). The reaction temperature was kept at a temperature of about 25 degrees Celsius. The resultant precipitate was then filtered and thoroughly washed with distilled de-ionized water at a temperature of about 55 degrees Celsius. The filtered solids were then washed with about 1200 ml of ethanol (about 70%). Following this last step, the solids were filtered and dispersed in ethanol (about 70%) to a total volume of about 675 ml in a stirred Parr reactor model number 4530. The reactor containing the resultant slurry was then fully purged with argon. Following this purge step, the reactor was pressurized with argon to a pressure of about 10 bar. Subsequently, the reactor was heated until the autogeneously generated pressure reached about 140 bar at which time, the reactor pressure was maintained at am autogeneously pressure from 130 to about 140 bar by venting whilst heating continued to a temperature of about 300 degrees Celsius. At that time, the reactor was vented to about 1 bar and heating continued until all the ethanol was substantially eliminated from the material and reactor. The reactor was then cooled to room temperature and the resultant powder material was calcined at about 950 degrees Celsius in air for about 5 hours. The resultant material is defined as material in the fresh state. The fresh material was then further calcined at one of about 1000, 1100, and about 1200 degrees Celsius, respectively, for about 10 hrs in air (see Table) for testing (defined as the aging conditions).

Example 9: 60 wt % ZrO.SUB.2.; 30 wt % CeO.SUB.2.; 6 wt % La.SUB.2.O.SUB.3.; 4 wt % Y.SUB.2.O.SUB.3

(19) A mixed oxide with the composition of oxide equivalent of about 60 wt % ZrO.sub.2, about 30 wt % CeO.sub.2, about 6 wt % La.sub.2O.sub.3, and about 4 wt % Y.sub.2O.sub.3 was synthesized by the following method. Solutions of zirconyl nitrate, cerium(III) nitrate, lanthanum nitrate and yttrium nitrate were combined in appropriate ratios to achieve the targeted elemental compositions of zirconium, cerium, lanthanum and yttrium. Distilled deionized water was then added to achieve a total oxide-based relative concentration of the metals of about 100 grams/liter. Following this adjustment, about 10 ml of hydrogen peroxide (H.sub.2O.sub.2, about 32 wt %) was added to the solution. This solution was then added slowly to a continuously stirred solution of ammonia water (about 1000 ml of about 4.5 molar NH.sub.4OH). The reaction temperature was kept at a temperature of about 25 degrees Celsius. The resultant precipitate was then filtered and thoroughly washed with distilled de-ionized water at a temperature of about 55 degrees Celsius. The filtered solids were then washed with about 1200 ml of isopropanol (about 99%). Following this last step, the solids were filtered and dispersed in isopropanol (about 99%) to a total volume of about 675 ml in a stirred Parr reactor model number 4530. The reactor containing the resultant slurry was then fully purged with argon. Following this purge step, the reactor was pressurized with argon to about 10 bar. Subsequently, the reactor was heated until the autogeneously generated pressure reached about 140 bar at which time, the reactor pressure was maintained at about 130 to about 140 bar by venting whilst heating continued to a temperature of about 300 degrees Celsius. At that time, the reactor was vented to about 1 bar and heating continued until substantially all of the isopropanol was eliminated from the material and reactor. The reactor was then cooled to room temperature and the resultant powder material was calcined at about 950 degrees Celsius in air for about 5 hours. The resultant material is defined as material in the fresh state. The fresh material was then further calcined at one of about 1000, about 1100, and about 1200 degrees Celsius, respectively, for about 10 hrs in air (see Table) for testing (defined as the aging conditions).

Example 10: 60 wt % ZrO.SUB.2.; 30 wt % CeO.SUB.2.: 6 wt % La.SUB.2.O.SUB.3.: 4 wt % Y.SUB.2.O.SUB.3

(20) A mixed oxide with the composition of oxide equivalent of about 60 wt % ZrO.sub.2, about 30 wt % CeO.sub.2, about 6 wt % La.sub.2O.sub.3, and about 4 wt % Y.sub.2O.sub.3 was synthesized by the following method. Solutions of zirconyl nitrate, ceric ammonium nitrate, lanthanum nitrate and yttrium nitrate were combined in appropriate ratios to achieve the targeted elemental compositions of zirconium, cerium, lanthanum and neodymium. Distilled deionized water was then added to achieve a total oxide-based relative concentration of the metals of about 100 grams/liter. This solution was then added slowly to a continuously stirred solution of ammonia water (about 1000 ml of about 4.5 molar NH.sub.4OH). The reaction temperature was kept at a temperature of about 25 degrees Celsius. The resultant precipitate was then filtered and thoroughly washed with distilled de-ionized water at a temperature of about 55 degrees Celsius. The filtered solids were then washed with about 1200 ml of ethanol (about 99%). Following this last step, the solids were filtered and dispersed in ethanol (about 99%) to a total volume of about 675 ml in a stirred Parr reactor model number 4530. The reactor containing the resultant slurry was then fully purged with argon. Following this purge step, the reactor was pressurized with argon to about 10 bar. Subsequently, the reactor was heated until the autogeneously generated pressure reached about 140 bar at which time, the reactor pressure was maintained at a pressure from about 130 to about 140 bar by venting whilst heating continued to a temperature of about 300 degrees Celsius. At that time, the reactor was vented to about 1 bar and heating continued until all the ethanol was eliminated from the material and reactor. The reactor was then cooled to room temperature and the resultant powder material was calcined at a temperature of about 950 degrees Celsius in air for about 5 hours. The fresh material was then further calcined at one of about 1000, about 1100, and about 1200 degrees Celsius, respectively, for about 10 hrs in air (see Table) for testing (defined as the aging conditions). FIG. 1 shows the H.sub.2 thermal programmed reduction components over a temperature range from about 100 to about 1100 degrees Celsius; two components are evident between 300 and 500 degrees Celsius, with one component at a temperature of 400 degrees Celsius or less and another at a temperature of more than 400 degrees Celsius.

(21) The porosity and total pore volume was measured using a Micromeritics Autopore IV 9500system. The procedures outlined in ASTM International test method D 4284-07 were followed; the sample size was 0.5 grams, the mercury contact angle was 130, the mercury surface tension was 0.485 N/m (4845 d/cm). The optimal pressure increase was a step-wise increase with a dwell time of 10 seconds/step. Additional details are given below. A graphical example of the cumulative pore volume distribution of the Example 1 resultant fresh material is shown in the FIG. 2, which shows the cumulative and differential pore volume distribution for the fresh material of Example 1.

(22) The apparent surface area of the material was determined by using a Micromeritics ASAP 2000 system and nitrogen at about 77 about Kelvin. The procedure outlined in ASTM International test method D 3663-03 (Reapproved 2008) was used but with one significant exception. It is well known that a BET Surface Area determination is not possible for materials that contain microporosity. Recognizing that the surface area is an approximation, the values reported are labeled apparent surface area values rather than BET surface area values. In compliance with commonly accepted procedures, the determination of apparent surface area, the application of the BET equation was limited to the pressure range where the term n.sub.a(1P/Po) of the equation continuously increases with P/Po. The out gassing of the sample was done under nitrogen at about 300 degrees Celsius for about 2 hours.

(23) The reducibility of each of the samples was done using an Altamira Instruments AMI-390 Temperature Programmed Reduction (TPR) apparatus using air as the oxidant gas and hydrogen as the reducing gas. The system was calibrated using 1% Re on 1% Co.sub.3O.sub.4 on alumina as a baseline material. The measurement procedure used was as

(24) TABLE-US-00001 TABLE Hydrogen TPR signal integral Total Pore area (100-1000 C.) Volume (cc/g) H.sub.2 Consumption H.sub.2 Consumption/ Apparent Surface Area (m.sup.2/g) after 1100 C./ Integral CeO.sub.2 Calcination for 10 hours Example Fresh 10 hrs (mol/g) Molar Ratio 1000 C. 1100 C. 1200 C. 1 1.33 0.65 1022 0.59 54 24 1.9 2 1.43 0.71 966 0.55 53 27 2.4 3 1.67 0.85 967 0.55 55 27 2.9 4 1.96 0.99 654 0.54 54 28 3.9 5 2.00 1.58 950 0.55 58 28 4 6 2.20 1.11 287 0.99 54 29 4.6 7 2.33 1.07 1163 0.67 55 26 3.6 8 2.60 1.17 63 28 4.1 9 3.23 1.46 1006 0.58 60 27 4.5 10 1.19 934 0.54 58 28 5.2
follows. At first a 0.05 gram of 1000 degrees Celsius of an aged sample was placed into the TPR machine sample tube. The sample tube was then connected to the apparatus and the sample was pre-oxidized at 400 C. in 25 cc/minute flowing O.sub.2/He (10:90 vol %) atmosphere for 15 min. Following this treatment, the sample was allowed to cool under the same gas flow. Once cooled to about 100 C., the flow of gas was changed to a H.sub.2/Ar mixture (5:95 vol %) with a flow rate of 25 cc/minute. The temperature was then ramped at 10 C./minute to 1000 C. whilst simultaneously monitoring the system output with TCD detectors. The total consumption of H.sub.2 relative to the CeO.sub.2 molar equivalent content in the sample is calculated.

(25) A number of variations and modifications of the disclosure can be used. It would be possible to provide for some features of the disclosure without providing others.

(26) The present disclosure, in various aspects, embodiments, and configurations, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various aspects, embodiments, configurations, sub-combinations, and subsets thereof. Those of skill in the art will understand how to make and use the various aspects, aspects, embodiments, and configurations, after understanding the present disclosure. The present disclosure, in various aspects, embodiments, and configurations, includes providing devices and processes in the absence of items not depicted and/or described herein or in various aspects, embodiments, and configurations hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and\or reducing cost of implementation.

(27) The foregoing discussion of the disclosure has been presented for purposes of illustration and description. The foregoing is not intended to limit the disclosure to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the disclosure are grouped together in one or more, aspects, embodiments, and configurations for the purpose of streamlining the disclosure. The features of the aspects, embodiments, and configurations of the disclosure may be combined in alternate aspects, embodiments, and configurations other than those discussed above. This method of disclosure is not to be interpreted as reflecting an intention that the claimed disclosure requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed aspects, embodiments, and configurations. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the disclosure.

(28) Moreover, though the description of the disclosure has included description of one or more aspects, embodiments, or configurations and certain variations and modifications, other variations, combinations, and modifications are within the scope of the disclosure, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative aspects, embodiments, and configurations to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter.