Diesel oxidation catalyst comprising platinum group metal nanoparticles
The present invention relates to diesel oxidation catalyst compositions and catalyst articles, wherein the compositions and articles include a plurality of platinum group nanoparticles substantially in fully reduced form, wherein the nanoparticles have an average particle size of about 1 to about 10 nm and at least about 90% of the nanoparticles have a particle size of +/− about 2 nm of the average particle size. Such compositions can further include a refractory metal oxide material, wherein the nanoparticles and refractory metal oxide material can be combined within the same coating on a substrate or can be applied sequentially on a substrate. The nanoparticles can advantageously be substantially free of halides, alkali metals, alkaline earth metals, sulfur compounds, and boron compounds. Methods of preparing and using such compositions and catalyst articles (e.g., for the treatment of diesel exhaust gas streams) are also provided herein.
1. A diesel oxidation catalyst composition, the composition comprising:
a plurality of platinum group metal nanoparticles selected from the group consisting of Pt, Pd, Au, Ag, Ru, Rh, Ir, Os, alloys thereof, and mixtures thereof,
wherein about 90% or more of the platinum group metal is in fully reduced form,
wherein the nanoparticles have an average particle size of about 1 to about 10 nm and at least about 90% of the nanoparticles have a particle size of +/− about 2 nm of the average particle size; and, optionally,
a refractory metal oxide material.
2. The diesel oxidation catalyst composition of claim 1 , wherein at least about 90% of the nanoparticles have a particle size+/− about 1 nm of the average particle size.
3. The diesel oxidation catalyst composition of claim 1 , wherein at least about 95% of the nanoparticles have a particle size+/−2 nm of the average particle size.
4. The diesel oxidation catalyst composition of claim 1 , wherein at least about 95% of the nanoparticles have a particle size+/− about 1 nm of the average particle size.
5. The diesel oxidation catalyst composition of claim 1 , wherein the average particle size of the nanoparticles is about 2 to about 3 nm.
6. The diesel oxidation catalyst composition of claim 1 , wherein the average particle size of the nanoparticles is about 3 to about 5 nm.
7. The diesel oxidation catalyst composition of claim 1 , wherein the average particle size of the nanoparticles is about 5 to about 7 nm.
8. The diesel oxidation catalyst composition of claim 1 , wherein the average particle size of the nanoparticles is about 7 to about 9 nm.
9. The diesel oxidation catalyst composition of claim 1 , wherein the composition does not comprise halides, alkali metals, alkaline-earth metals, sulfur compounds, or boron compounds.
10. The diesel oxidation catalyst composition of claim 1 , wherein the composition does not comprise boron or sodium.
11. The diesel oxidation catalyst composition of claim 1 , wherein the platinum group metal nanoparticles comprise platinum.
12. The diesel oxidation catalyst composition of claim 1 , wherein the refractory metal oxide is selected from the group consisting of alumina, silica, zirconia, titania, ceria, and physical mixtures or chemical combinations thereof.
13. The diesel oxidation catalyst composition of claim 1 , wherein the refractory metal oxide is a silica-doped alumina, silica-doped titania, or silica-doped zirconia.
14. The diesel oxidation catalyst composition of claim 13 , wherein the refractory metal oxide comprises 1-10% SiO 2 -doped Al 2 O 3 , 1-20% SiO 2 -doped TiO 2 , or 1-30% SiO 2 -doped ZrO 2 .
15. The diesel oxidation catalyst composition of claim 13 , wherein the refractory metal oxide comprises 1% SiO 2 -doped Al 2 O 3 or 8-14% SiO 2 -doped TiO 2 .
16. A diesel oxidation catalyst article, comprising a substrate having a coating comprising the diesel oxidation catalyst composition of claim 1 disposed thereon.
17. The diesel oxidation catalyst article of claim 16 , wherein the refractory metal oxide material is present as a layer overlying the substrate and positioned between the substrate and the coating.
18. A method of treating an exhaust stream from a diesel engine, comprising passing the exhaust stream through the diesel oxidation catalyst article of claim 16 such that NO is oxidized within the catalyst article.
19. An emission treatment system for treatment of an exhaust gas stream, the emission treatment system comprising:
a diesel engine producing an exhaust gas stream;
a diesel oxidation catalyst article according to claim 16 positioned in fluid communication with the exhaust gas stream and adapted for oxidation of carbon monoxide and hydrocarbon gases within the exhaust stream to form a treated exhaust gas stream; and
at least one additional catalyst article downstream from the diesel oxidation catalyst article and in fluid communication with the treated exhaust gas stream, the at least one additional catalyst article adapted for ammonia oxidation, particulate filtration, NOx storage, NOx trapping, selective catalytic reduction of NOx, or combinations thereof.
20. A catalyzed soot filter article, comprising a substrate having a coating comprising the diesel oxidation catalyst composition of claim 1 disposed thereon.
21. A method of making a catalyst article comprising platinum group metal nanoparticles, comprising:
applying a refractory metal oxide slurry and a colloidal dispersion comprising platinum group metal nanoparticles chosen from the group consisting of Pt, Pd, Au, Ag, Ru, Rh, Ir, Os, alloys thereof, and mixtures thereof to a substrate;
wherein about 90% or more of the platinum group metal is in fully reduced form;
wherein the nanoparticles have an average particle size of about 1 to about 10 nm; and
wherein at least about 90% of the nanoparticles have a particle size of +/− about 2 nm of the average particle size.
22. The method of claim 21 , wherein the catalyst article is a diesel oxidation catalyst article or a catalyzed soot filter article.
23. The method of claim 21 , further comprising calcining the coated substrate after the applying step.
24. The method of claim 21 , further comprising forming a washcoat slurry comprising the refractory metal oxide slurry in water and the colloidal dispersion and applying the refractory metal oxide slurry and the colloidal dispersion to the substrate in the form of the washcoat.
25. The method of claim 21 , comprising:
applying the refractory metal oxide slurry to the substrate;
calcining the refractory metal oxide coating on the substrate; and
thereafter applying the colloidal dispersion overlying the calcined refractory metal oxide coating.
26. The method of claim 21 , wherein the platinum group metal nanoparticles comprise platinum.
27. The method of claim 21 , wherein the refractory metal oxide is selected from the group consisting of alumina, silica, zirconia, titania, ceria, and physical mixtures or chemical combinations thereof.
28. The method of claim 21 , wherein the refractory metal oxide is a silica-doped alumina, silica-doped titania, or silica-doped zirconia.
29. The method of claim 21 , wherein the refractory metal oxide comprises 1-10% SiO 2 -doped Al 2 O 3 , 1-20% SiO 2 -doped TiO 2 , or 1-30% SiO 2 -doped ZrO 2 .
30. The method of claim 21 , wherein the refractory metal oxide comprises 1% SiO 2 -doped Al 2 O 3 or 8-14% SiO 2 -doped TiO 2 .
31. The method of claim 21 , wherein at least about 90% of the nanoparticles have a particle size+/− about 1 nm of the average particle size.
32. The method of claim 21 , wherein at least about 95% of the nanoparticles have a particle size+/−2 nm of the average particle size.
33. The method of claim 21 , wherein at least about 95% of the nanoparticles have a particle size+/− about 1 nm of the average particle size.
34. The method of claim 21 , wherein the average particle size of the nanoparticles is about 2 to about 3 nm.
35. The method of claim 21 , wherein the average particle size of the nanoparticles is about 3 to about 5 nm.
36. The method of claim 21 , wherein the average particle size of the nanoparticles is about 5 to about 7 nm.
37. The method of claim 21 , wherein the average particle size of the nanoparticles is about 7 to about 9 nm.
38. The method of claim 21 , wherein the coating does not comprise halides, alkali metals, alkaline-earth-metals, sulfur compounds, and boron compounds.
39. The method of claim 21 , further comprising aging the catalyst article by subjecting the article to heat treatment at 550-600° C. wherein at least about 50% of the PGM particles after aging have diameters of about 1 to 50 nm.
40. The method of claim 21 , further comprising aging the catalyst article by subjecting the article to heat treatment at 550-600° C. wherein at least about 75% of the PGM particles after aging have diameters of about 1 to 50 nm.
41. The method of claim 21 , further comprising aging the catalyst article by subjecting the article to heat treatment at 550-600° C. wherein at least about 50% of the PGM particles after aging have diameters of about 1 to 25 nm.
42. The method of claim 21 , further comprising preparing the platinum group metal nanoparticles by a method comprising:
a) preparing a solution of platinum group metal precursors selected from salts of a metal selected from the group consisting of Pt, Pd, Au, Ag, Ru, Rh, Ir, Os and alloys thereof in the presence of a dispersion medium and a water soluble polymer suspension stabilizing agent, wherein the platinum group metal precursors do not comprise halides, alkali metals, alkaline-earth metals, sulfur compounds, and boron compounds; and
b) combining the solution with a reducing agent to provide a platinum group metal nanoparticle colloidal dispersion ‘wherein the nanoparticle concentration is at least about 2 wt. % of the total weight of the colloidal dispersion’ and wherein at least about 90% of the platinum group metal in the colloidal dispersion is in fully reduced form.