Cerium containing nanoparticles prepared in non-polar solvent

• US 8,980,202 B2
• Filed: 11/14/2011
• Issued: 03/17/2015
• Est. Priority Date: 11/12/2010
• Status: Active Grant

• Current Assignee: Cerion, LLC (Revstone Industries LLC)
• Original Assignee: Peter Jerome Cowdery-Corvan
• Inventors: Cowdery-Corvan, Peter Jerome, Irving, Lyn Marie, Hailstone, Richard Kenneth, Reed, Kenneth Joseph, Allston, Thomas Dale, Augustyn, Carly Louise
• Primary Examiner(s): BOS, STEVEN J
• Application Number:
  US13/295,382
• Publication Number:
  US 20120117863A1
• Time in Patent Office: 1,219 Days
• Field of Search: 423/263, 423/275, 502/304
• US Class Current: 423/21.1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01F 17/235 Cerium oxides or hydroxides
• CPC Class Codes: C01F 17/32 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
• CPC Class Codes: C01G 25/00 Compounds of zirconium
• CPC Class Codes: C01G 49/0054 containing one rare earth metal, yttrium or scandium
• CPC Class Codes: C01P 2002/54 one element only
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer

Abstract

A method of making cerium-containing metal oxide nanoparticles in non-polar solvent eliminates the need for solvent shifting steps. The direct synthesis method involves: (a) forming a reaction mixture of a source of cerous ion and a carboxylic acid, and optionally, a hydrocarbon solvent; and optionally further comprises a non-cerous metal ion; (b) heating the reaction mixture to oxidize cerous ion to ceric ion; and (c) recovering a nanoparticle of either cerium oxide or a mixed metal oxide comprising cerium. The cerium-containing oxide nanoparticles thus obtained have cubic fluorite crystal structure and a geometric diameter in the range of about 1 nanometer to about 20 nanometers. Dispersions of cerium-containing oxide nanoparticles prepared by this method can be used as a component of a fuel or lubricant additive.

Claims

1. A method of making a cerium-containing metal oxide nanoparticle, comprising:

a) forming a reaction mixture of a source of cerous ion and a solvent, and optionally further comprising a non-cerous metal ion, wherein the solvent consists essentially of;

(1) a carboxylic acid, wherein said carboxylic acid is a C₃-C₂₂ paraffinic carboxylic acid, a monoether carboxylic acid, a polyether carboxylic acid, or a mixture thereof, and (2) an optional hydrocarbon; and

b) heating the reaction mixture to form a product dispersion containing cerium-containing metal oxide nanoparticles and less than about 0.5 wt. % water.

2. The method of claim 1, wherein said cerium-containing metal oxide nanoparticle is of cubic fluorite crystal structure and has a geometric diameter of about 1 nanometer to about 20 nanometers.

3. The method of claim 1, wherein said non-cerous metal ion is present in the reaction mixture, and said non-cerous metal ion is iron, zirconium, or a combination thereof.

4. The method of claim 1, wherein said carboxylic acid is a C₃-C₂₂ paraffinic carboxylic acid.

5. The method of claim 4, wherein said paraffinic carboxylic acid is octanoic acid.

6. The method of claim 1, wherein said carboxylic acid is a monoether carboxylic acid.

7. The method of claim 6, wherein said monoether carboxylic acid is methoxyacetic acid.

8. The method of claim 1, wherein said carboxylic acid is a polyether carboxylic acid.

9. The method of claim 8, wherein said polyether carboxylic acid is 2-(2-methoxyethoxyl)acetic acid or 2-[2-(2-methoxyethoxy)ethoxy]acetic acid.

10. The method of claim 1, wherein said hydrocarbon solvent is present in the reaction mixture, and said hydrocarbon solvent is a C₅-C₂₅ paraffin, an olefin, an isoparaffin distillate, or a hydrotreated petroleum distillate.

11. The method of claim 10, wherein said paraffin is a straight chain, a branched or a cyclic paraffin.

12. The method of claim 10, wherein said olefin is 1-octadecene.

13. The method of claim 1, wherein the reaction mixture is heated from about 100°

C. to about 250°

C.

20. The method of claim 1, wherein said cerium-containing metal oxide nanoparticles have a geometric diameter of less than about 2 nm.

14. A method of making cerium-containing metal oxide nanoparticles, comprising:

a) forming a reaction mixture comprising a source of cerous ion, an optional source of one or more non-cerous metal ions (M), and a solvent consisting essentially of a carboxylic acid and a hydrocarbon; and

b) heating the reaction mixture to oxidize cerous ion to ceric ion, thereby forming a product dispersion comprising cerium-containing metal oxide nanoparticles,

wherein the product dispersion comprises less than about 0.5 wt. % water.

15. The method of claim 14, wherein said non-cerous metal ion is iron and/or zirconium.

16. The method of claim 14, wherein said carboxylic acid is a C₃-C₂₂ paraffinic or olefinic carboxylic acid.

17. The method of claim 14, wherein said carboxylic acid is selected from the group consisting of:

octanoic acid, oleic acid, methoxyacetic acid, 2-(2-methoxyethoxyl)acetic acid, 2-[2-(2-methoxyethoxyl)ethoxy]acetic acid, and mixtures thereof.

18. The method of claim 14, wherein said hydrocarbon solvent is a C₅-C₂₅ paraffin, an olefin, an isoparaffin distillate, or a hydrotreated petroleum distillate.

19. The method of claim 18, wherein said olefin is 1-octadecene.

21. The method of claim 14, wherein said cerium-containing metal oxide nanoparticles have a geometric diameter of less than about 2 nm.