# US 9,517,448 B2 · Compositions of lean NOx trap (LNT) systems and methods of making and using same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,517,448 B2 - Document ID: US9517448B2 - Status: Granted - Kind: B2 - Application number: 14/521,334 - Filed: 2014-10-22 - Published: 2015-06-18 - Granted: 2016-12-13 - Earliest claimed: 2013-10-22 - Assignees: SDCmaterials, Inc. - Applicants: SDCmaterials, Inc. - Inventors: Bryant Kearl; Qinghua Yin; Xiwang Qi; David Leamon; Maximilian A. Biberger - Web page: https://patentgrep.com/patent/US9517448B2 ## CPC - B01J 23/464: {Rhodium} - B01D 53/9422: {for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)} - B01D 53/9431: {Processes characterised by a specific device} - B01J 23/02: of the alkali- or alkaline earth metals or beryllium - B01J 23/10: of rare earths - B01J 23/44: Palladium - B01J 23/63: with rare earths or actinides - B01J 35/19: {Catalysts containing parts with different compositions} - B01J 35/45: Nanoparticles - B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying} - B01J 37/0244: {Coatings comprising several layers} - B01J 37/0248: {Coatings comprising impregnated particles} - B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)} - B01J 37/349: {making use of flames, plasmas or lasers} - F01N 3/10: by thermal or catalytic conversion of noxious components of exhaust - B01D 2255/1021: Platinum - B01D 2255/1023: Palladium - B01D 2255/1025: Rhodium - B01D 2255/104: Silver - B01D 2255/2061: Yttrium - B01D 2255/2063: Lanthanum - B01D 2255/2065: Cerium - B01D 2255/20715: Zirconium - B01D 2255/20738: Iron - B01D 2255/20776: Tungsten - B01D 2255/20792: Zinc - B01D 2255/40: Mixed oxides - B01D 2255/407: Zr-Ce mixed oxides - B01D 2255/908: O2-storage component incorporated in the catalyst - B01D 2255/91: NOx-storage component incorporated in the catalyst - B01D 2255/9202: Linear dimensions - B01J 35/733: {Perovskite-type} - F01N 2370/02: used in catalytic reactors - F01N 2570/14: Nitrogen oxides - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - F01N: GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES (arrangements in connection with gas exhaust of propulsion units in vehicles B60K13/00; combustion-air intake silencers specially adapted for, or arranged on, internal-combustion engines F02M35/00; protecting against, or damping, noise in general G10K11/16) ## Abstract The present disclosure relates to a substrate comprising nanoparticle catalysts and NOx storage materials for treatment of gases, and washcoats for use in preparing such a substrate. Also provided are methods of preparation of the nanoparticle catalysts and NOx storage materials, as well as methods of preparation of the substrate comprising the nanoparticle catalysts and NOx storage materials. More specifically, the present disclosure relates to a coated substrate comprising nanoparticle catalysts and NOx storage materials for lean NOx trap (LNT) systems, useful in the treatment of exhaust gases. ## Claims ### Claim 1 A coated substrate comprising: a substrate; a washcoat layer comprising oxidative catalytically active micron-particles, the oxidative catalytically active micron-particles comprising oxidative composite nanoparticles bonded to a first micron-sized carrier particle, the oxidative composite nanoparticles comprising a first support nanoparticle and an oxidative catalytic nanoparticle; a washcoat layer comprising reductive catalytically active micron-particles, the reductive catalytically active micron-particles comprising reductive composite nanoparticles bonded to a second micron-sized carrier particle, the reductive composite nanoparticles comprising a second support nanoparticle and a reductive catalytic nanoparticle; and a washcoat layer comprising NOx trapping particles, the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 2 (depends on 1) The coated substrate of claim 1, wherein the micron-sized cerium oxide-containing material comprises cerium oxide, cerium-zirconium oxide, cerium-lanthanum oxide, cerium-yttrium oxide, cerium-zirconium-lanthanum oxide, cerium-zirconium-yttrium oxide, cerium-lanthanum-yttrium oxide, or cerium-zirconium-lanthanum-yttrium oxide. ### Claim 3 (depends on 2) The coated substrate of claim 2, wherein the micron-sized cerium oxide-containing material comprises cerium-zirconium-lanthanum oxide or cerium-zirconium-lanthanum-yttrium oxide. ### Claim 4 (depends on 1) The coated substrate of claim 1, wherein the washcoat layer comprising reductive catalytically active micron-particles is located closer to the substrate than the washcoat layer comprising oxidative catalytically active micron-particles. ### Claim 5 (depends on 4) The coated substrate of claim 4, wherein the washcoat layer comprising oxidative catalytically active micron-particles is located closer to the substrate than the washcoat layer comprising NOx trapping particles. ### Claim 6 (depends on 1) The coated substrate of claim 1, wherein the NOx trapping particles further comprise barium oxide impregnated in the micron-sized cerium oxide-containing material. ### Claim 7 (depends on 6) The coated substrate of claim 6, wherein the barium oxide is impregnated in the micron-sized cerium oxide or the micron-sized cerium oxide-containing material by wet chemistry. ### Claim 8 (depends on 1) The coated substrate of claim 1, wherein the NOx trapping particles further comprise platinum or palladium impregnated in the micron-sized cerium oxide-containing material. ### Claim 9 (depends on 8) The coated substrate of claim 8, wherein the platinum or palladium is plasma-generated. ### Claim 10 (depends on 8) The coated substrate of claim 8, wherein the platinum or palladium is impregnated in the micron-sized cerium oxide-containing material by wet chemistry. ### Claim 11 (depends on 1) The coated substrate of claim 1, wherein the NOx trapping particles further comprise the perovskite FeBaO3 impregnated in the micron-sized cerium oxide-containing material. ### Claim 12 (depends on 1) The coated substrate of claim 1, wherein the NOx trapping particles further comprise metal oxides selected from the group consisting of samarium, zinc, copper, iron, and silver oxides impregnated in the micron-sized cerium oxide-containing material. ### Claim 13 (depends on 1) The coated substrate of claim 1, wherein the washcoat layer comprising NOx trapping particles further comprises micron-sized aluminum oxide particles. ### Claim 14 (depends on 1) The coated substrate claim 1, wherein the oxidative catalytically active micron-particles comprise a material selected from the group comprising platinum, palladium, or a platinum-palladium alloy. ### Claim 15 (depends on 1) The coated substrate of claim 1, wherein the NOx trapping particles further comprise zirconium oxide. ### Claim 16 (depends on 1) The coated substrate of claim 1, wherein the first micron-sized carrier particle, first micron-sized porous carrier, or first support particle comprises aluminum oxide. ### Claim 17 (depends on 1) The coated substrate of claim 1, wherein the second micron-sized carrier particle, second micron-sized porous carrier, or second support particle comprises cerium oxide. ### Claim 18 (depends on 1) The coated substrate of claim 1, wherein the washcoat layer comprising oxidative catalytically active micron-particles or the washcoat layer comprising reductive catalytically active micron-particles further comprises filler particles or boehmite particles; wherein the filler particles are metal oxide particles. ### Claim 19 (depends on 1) The coated substrate according to claim 1, wherein the micron-sized cerium oxide-containing material comprises cerium oxide. ### Claim 20 (depends on 1) A catalytic converter comprising a coated substrate of claim 1. ### Claim 21 (depends on 20) An exhaust treatment system comprising a conduit for exhaust gas and a catalytic converter according to claim 20. ### Claim 22 (depends on 21) A vehicle comprising an exhaust treatment system according to claim 21. ### Claim 23 (depends on 20) A vehicle comprising a catalytic converter according to claim 20. ### Claim 24 (depends on 1) A method of treating an exhaust gas, comprising contacting the coated substrate of claim 1 with the exhaust gas. ### Claim 25 (depends on 1) A method of treating an exhaust gas, comprising contacting the coated substrate of claim 1 with the exhaust gas, wherein the substrate is housed within a catalytic converter configured to receive the exhaust gas. ### Claim 26 A coated substrate comprising: a substrate; a washcoat layer comprising oxidative catalytically active micron-particles, the oxidative catalytically active micron-particles comprising oxidative composite nanoparticles embedded in a first micron-sized porous carrier, the oxidative composite nanoparticles comprising a first support nanoparticle and an oxidative catalytic nanoparticle; a washcoat layer comprising reductive catalytically active micron-particles, the reductive catalytically active micron-particles comprising reductive composite nanoparticles embedded in a second micron-sized porous carrier, the reductive composite nanoparticles comprising a second support nanoparticle and a reductive catalytic nanoparticle; and a washcoat layer comprising NOx trapping particles, and the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 27 (depends on 26) The coated substrate of claim 26, wherein the micron-sized cerium oxide-containing material comprises cerium oxide, cerium-zirconium oxide, cerium-lanthanum oxide, cerium-yttrium oxide, cerium-zirconium-lanthanum oxide, cerium-zirconium-yttrium oxide, cerium-lanthanum-yttrium oxide, or cerium-zirconium-lanthanum-yttrium oxide. ### Claim 28 (depends on 27) The coated substrate of claim 27, wherein the micron-sized cerium oxide-containing material comprises cerium-zirconium-lanthanum oxide or cerium-zirconium-lanthanum-yttrium oxide. ### Claim 29 (depends on 26) The coated substrate of claim 26, wherein the washcoat layer comprising reductive catalytically active micron-particles is located closer to the substrate than the washcoat layer comprising oxidative catalytically active micron-particles. ### Claim 30 (depends on 29) The coated substrate of claim 29, wherein the washcoat layer comprising oxidative catalytically active micron-particles is located closer to the substrate than the washcoat layer comprising NOx trapping particles. ### Claim 31 (depends on 26) The coated substrate of claim 26, wherein the NOx trapping particles further comprise barium oxide impregnated in the micron-sized cerium oxide-containing material. ### Claim 32 (depends on 31) The coated substrate of claim 31, wherein the barium oxide is impregnated in the micron-sized cerium oxide or the micron-sized cerium oxide-containing material by wet chemistry. ### Claim 33 (depends on 26) The coated substrate of claim 26, wherein the NOx trapping particles further comprise platinum or palladium impregnated in the micron-sized cerium oxide-containing material. ### Claim 34 (depends on 33) The coated substrate of claim 33, wherein the platinum or palladium is plasma-generated. ### Claim 35 (depends on 33) The coated substrate of claim 33, wherein the platinum or palladium is impregnated in the micron-sized cerium oxide-containing material by wet chemistry. ### Claim 36 (depends on 26) The coated substrate of claim 26, wherein the NOx trapping particles further comprise the perovskite FeBaO3 impregnated in the micron-sized cerium oxide-containing material. ### Claim 37 (depends on 26) The coated substrate of claim 26, wherein the NOx trapping particles further comprise metal oxides selected from the group consisting of samarium, zinc, copper, iron, and silver oxides impregnated in the micron-sized cerium oxide-containing material. ### Claim 38 (depends on 26) The coated substrate of claim 26, wherein the washcoat layer comprising NOx trapping particles further comprises micron-sized aluminum oxide particles. ### Claim 39 (depends on 26) The coated substrate claim 26, wherein the oxidative catalytically active micron-particles comprise a material selected from the group comprising platinum, palladium, or a platinum-palladium alloy. ### Claim 40 (depends on 26) The coated substrate of claim 26, wherein the NOx trapping particles further comprise zirconium oxide. ### Claim 41 (depends on 26) The coated substrate of claim 26, wherein the first micron-sized carrier particle, first micron-sized porous carrier, or first support particle comprises aluminum oxide. ### Claim 42 (depends on 26) The coated substrate of claim 26, wherein the second micron-sized carrier particle, second micron-sized porous carrier, or second support particle comprises cerium oxide. ### Claim 43 (depends on 26) The coated substrate of claim 26, wherein the washcoat layer comprising oxidative catalytically active micron-particles or the washcoat layer comprising reductive catalytically active micron- particles further comprises filler particles or boehmite particles; wherein the filler particles are metal oxide particles. ### Claim 44 (depends on 26) The coated substrate according to claim 26, wherein the micron-sized cerium oxide-containing material comprises cerium oxide. ### Claim 45 (depends on 26) A catalytic converter comprising a coated substrate of claim 26. ### Claim 46 (depends on 45) An exhaust treatment system comprising a conduit for exhaust gas and a catalytic converter according to claim 45. ### Claim 47 (depends on 46) A vehicle comprising a catalytic converter according to claim 46. ### Claim 48 (depends on 47) A vehicle comprising an exhaust treatment system according to claim 47. ### Claim 49 (depends on 26) A method of treating an exhaust gas, comprising contacting the coated substrate of claim 26 with the exhaust gas. ### Claim 50 (depends on 26) A method of treating an exhaust gas, comprising contacting the coated substrate of claim 26 with the exhaust gas, wherein the substrate is housed within a catalytic converter configured to receive the exhaust gas. ### Claim 51 A coated substrate comprising: a substrate; a washcoat layer comprising oxidative catalytically active composite nanoparticles attached to a first micron-sized support particle, the oxidative catalytically active composite nanoparticles being plasma-generated and comprising a first support nanoparticle and an oxidative catalytic nanoparticle; a washcoat layer comprising reductive catalytically active composite nanoparticles attached to a second micron-sized support particle, the reductive catalytically active composite nanoparticles being plasma-generated and comprising a second support nanoparticle and a reductive catalytic nanoparticle; and a washcoat layer comprising NOx trapping particles, and the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 52 (depends on 51) The coated substrate according to claim 51, wherein the micron-sized cerium oxide-containing material comprises cerium oxide. ### Claim 53 A method of forming a coated substrate, the method comprising: a) coating a substrate with a washcoat composition comprising oxidative catalytically active micron-particles, the oxidative catalytically active micron-particles comprising composite oxidative nanoparticles bonded to a first micron-sized carrier particle, the oxidative composite nanoparticles comprising a first support nanoparticle and an oxidative catalytic nanoparticle; b) coating the substrate with a washcoat composition comprising reductive catalytically active micron-particles, the reductive catalytically active micron-particles comprising reductive composite nanoparticles bonded to a second micron-sized carrier particle, the reductive composite nanoparticles comprising a second support nanoparticle and a reductive catalytic nanoparticle; and c) coating the substrate with a washcoat composition comprising NOx trapping particles, the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 54 A method of forming a coated substrate, the method comprising: a) coating a substrate with a washcoat composition comprising oxidative catalytically active micron-particles, the oxidative catalytically active micron-particles comprising oxidative composite nanoparticles embedded in a first micron-sized porous carrier, the oxidative composite nanoparticles comprising a first support nanoparticle and an oxidative catalytic nanoparticle; b) coating the substrate with a washcoat composition comprising reductive catalytically active micron-particles, the reductive catalytically active micron-particles comprising reductive composite nanoparticles embedded in a second micron-sized porous carrier, the reductive composite nanoparticles comprising a second support nanoparticle and reductive catalytic nanoparticle; and c) coating the substrate with a washcoat composition comprising NOx trapping particles, the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 55 A method of forming a coated substrate, the method comprising: a) coating a substrate with a washcoat composition comprising oxidative catalytically active composite nanoparticles attached to a first micron-sized support particle, the oxidative catalytically active composite nanoparticles being plasma-generated and comprising a first support nanoparticle and an oxidative catalytic nanoparticle; b) coating the substrate with a washcoat composition comprising reductive catalytically active composite nanoparticles attached to a second micron-sized support particle, the reductive catalytically active composite nanoparticles being plasma-generated and comprising a second support nanoparticle and a reductive catalytic nanoparticle; and c) coating the substrate with a washcoat composition comprising NOx trapping particles, the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 56 A coated substrate comprising: a substrate; a first washcoat layer comprising oxidative catalytically active micron-particles, the oxidative catalytically active micron-particles comprising oxidative composite nanoparticles bonded to a first micron-sized carrier particle, the oxidative composite nanoparticles comprising a first support nanoparticle and an oxidative catalytic nanoparticle; and a second washcoat layer comprising reductive catalytically active micron-particles and NOx trapping particles, the reductive catalytically active micron-particles comprising reductive composite nanoparticles bonded to a second micron-sized carrier particle, the reductive composite nanoparticles comprising a second support nanoparticle and a reductive catalytic nanoparticle, and the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 57 A coated substrate comprising: a substrate; a washcoat layer comprising oxidative catalytically active micron-particles, the oxidative catalytically active micron-particles comprising oxidative composite nanoparticles embedded in a first micron-sized porous carrier, the oxidative composite nanoparticles comprising a first support nanoparticle and an oxidative catalytic nanoparticle; and a washcoat layer comprising reductive catalytically active micron- particles and NOx trapping particles, the reductive catalytically active micron-particles comprising reductive composite nanoparticles embedded in a second micron-sized porous carrier, the reductive composite nanoparticles comprising a second support nanoparticle and a reductive catalytic nanoparticle, and the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 58 A coated substrate comprising: a substrate; a washcoat layer comprising oxidative catalytically active composite nanoparticles attached to a first micron-sized support particle, the oxidative catalytically active composite nanoparticles being plasma-generated and comprising a first support nanoparticle and an oxidative catalytic nanoparticle; and a washcoat layer comprising NOx trapping particles and reductive catalytically active composite nanoparticles attached to a second micron-sized support particle, the reductive catalytically active composite nanoparticles being plasma-generated and comprising a second support nanoparticle and a reductive catalytic nanoparticle, and the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 59 A method of forming a coated substrate, the method comprising: a) coating a substrate with a washcoat composition comprising oxidative catalytically active micron-particles, the oxidative catalytically active micron-particles comprising oxidative composite nanoparticles bonded to a first micron-sized carrier particle, the oxidative composite nanoparticles comprising a first support nanoparticle and an oxidative catalytic nanoparticle; and b) coating the substrate with a washcoat composition comprising reductive catalytically active micron-particles and NOx trapping particles, the reductive catalytically active micron-particles comprising reductive composite nanoparticles bonded to second micron-sized carrier particle, the reductive composite nanoparticles comprising a second support nanoparticle and a reductive catalytic nanoparticle, and the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 60 A method of forming a coated substrate, the method comprising: a) coating a substrate with a washcoat composition comprising oxidative catalytically active micron-particles, the oxidative catalytically active micron-particles comprising oxidative composite nanoparticles embedded in a first micron-sized porous carrier, the oxidative composite nanoparticles comprising a first support nanoparticle and an oxidative catalytic nanoparticle; and b) coating the substrate with a washcoat composition comprising reductive catalytically active micron-particles and NOx trapping particles, the reductive catalytically active micron-particles comprising reductive composite nanoparticles embedded in a second micron-sized porous carrier, the reductive composite nanoparticles comprising a second support nanoparticle and a reductive catalytic nanoparticle, and the NOx trapping particles comprising a micron-sized cerium oxide-containing material. ### Claim 61 A method of forming a coated substrate, the method comprising: a) coating a substrate with a washcoat composition comprising oxidative catalytically active composite nanoparticles attached to a first micron-sized support particle, the oxidative catalytically active composite nanoparticles being plasma-generated and comprising a first support nanoparticle and an oxidative catalytic nanoparticle; and b) coating the substrate with a washcoat composition comprising NOx trapping particles and reductive catalytically active composite nanoparticles attached to a second micron-sized support particle, the reductive catalytically active composite nanoparticles being plasma-generated and comprising a second support nanoparticle and a reductive catalytic nanoparticle, and the NOx trapping particles comprising a micron-sized cerium oxide-containing material.