WO2023148470A1 - Surface-modified alumina composition for gasoline exhaust gas applications comprising perovskite-type compound - Google Patents

Surface-modified alumina composition for gasoline exhaust gas applications comprising perovskite-type compound Download PDF

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Publication number
WO2023148470A1
WO2023148470A1 PCT/GB2023/050057 GB2023050057W WO2023148470A1 WO 2023148470 A1 WO2023148470 A1 WO 2023148470A1 GB 2023050057 W GB2023050057 W GB 2023050057W WO 2023148470 A1 WO2023148470 A1 WO 2023148470A1
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Prior art keywords
alumina
composition
hours
heating
ion
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PCT/GB2023/050057
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English (en)
French (fr)
Inventor
Michael Howard
Jing Lu
Qinghe ZHENG
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Johnson Matthey PLC
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Johnson Matthey PLC
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Priority to CN202380014852.3A priority Critical patent/CN118338961A/zh
Priority to JP2024533865A priority patent/JP2025505489A/ja
Publication of WO2023148470A1 publication Critical patent/WO2023148470A1/en
Anticipated expiration legal-status Critical
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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Definitions

  • the invention relates to a composition comprising alumina, the alumina being surface- modified with a perovskite type compound, methods of manufacturing such a composition, compositions obtained or obtainable by such methods, a catalyst article, an emissions treatment system and a method of treating an exhaust gas.
  • a three-way catalyst (TWC) allows simultaneous conversions ( ⁇ 98%) of CO, HCs and NO x from gasoline engine exhaust to innocuous compounds at stoichiometric air-to-fuel ratio.
  • PGM platinum group metal
  • Rh platinum group metal
  • Modern TWCs use supported platinum group metal (hereinafter “PGM”) catalysts (Pd, Rh, Pt, etc.) deposited on a single, double or multilayer support, with the support material consisting of metal oxides with high specific surface area, primarily stabilized alumina and ceria-containing oxygen storage materials.
  • PGM platinum group metal
  • Cerium oxide (Ce x O y ), well known for its high oxygen storage capacity (OSC) due to the function of the Ce 4+ /Ce 3+ redox pair, plays an important role in TWC performance.
  • Ce x O y can also assist the feed-back control of stoichiometric condition by uptaking or donating oxygen during fuel lean/rich perturbations.
  • ZrO 2 zirconium oxide
  • OSC formulas are also added to OSC formulas to further enhance the TWC performance.
  • ABO 3- ⁇ perovskite-type materials are known in the art and can exhibit significant swings in oxygen non-stoichiometry ⁇ through the reaction with gas phase oxygen.
  • Perovskites with advanced compositions also present OSC capacity and intrinsic TWC activity.
  • OSC and catalytic activity of perovskite oxides are largely dependent on the nature of the B-site cation, while the A-site cation is found to be important in the perovskite structural formation by influencing vacancy density and charge-valence balance.
  • the oxygen uptake and release are associated with the existence of structural defects and the change of oxidation state of the B-site cation.
  • suprafacial oxygen species ⁇
  • ⁇ bulk oxygen from the lattice
  • interfacial oxygen ⁇
  • incorporation of PGM metal into the perovskite structure has been reported to yield an “intelligent catalyst” (PGM migration between bulk and surface at redox conditions), which leads to potential mitigation of metal sintering at severe automotive conditions.
  • perovskites for emissions abatement emerged from their reduced ability to develop large surface areas (i.e. they have low surface-area-to- volume ratio). Moreover, they drastically sinter above 600 °C, sometimes accompanied by phase transition/separation under redox conditions.
  • A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd;
  • A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd;
  • B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb, V, W, Bi, Zn, Sn, Pt, Rh, Pd, Ru,
  • A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd;
  • A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd;
  • B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb, V, W, Bi, Zn, Sn, Pt, Rh, Pd, Ru, Au, Ag,
  • Another aspect of the present disclosure is directed to a composition obtained or obtainable by the method of the above aspect.
  • Another aspect of the present disclosure is directed to a method of manufacturing a composition comprising alumina, the alumina being surface-modified with a perovskite type compound of formula (I); wherein formula (I) is defined by A x-y A’ y B 1-z B’ z O 3 ; where: A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb
  • Another aspect of the present disclosure is directed to a composition obtained or obtainable by the method of the above aspect.
  • Another aspect of the present disclosure is directed to a method of manufacturing a composition comprising alumina, the alumina being surface-modified with a perovskite type compound of formula (I); wherein formula (I) is defined by A x-y A’ y B 1-z B’ z O 3 ; where: A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb
  • Another aspect of the present disclosure is directed to a composition obtained or obtainable by the method of the above aspect.
  • Another aspect of the present invention is directed to a method of manufacturing a composition comprising alumina, the alumina being surface-modified with a perovskite type compound of formula (I); wherein formula (I) is defined by A x-y A’ y B 1-z B’ z O 3 ; where: A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb
  • FIG.1 shows a powder XRD pattern of 20% BaMnO 3 modified alumina according the Example A6.
  • FIG. 2 shows the selected STEM elemental mapping and images of 20% La 0.9 MnO 3 modified alumina according to Example A11.
  • FIG. 3 shows the selected STEM elemental mapping and images of 20% BaMnO 3 modified alumina according to Example A6.
  • FIG. 4 shows OSC of selected perovskite-modified alumina samples.
  • FIG. 5a shows perturbated aged TWC light off performance for NO x conversions of washcoated (B1) Reference Pd catalyst (aged) on single alumina support, and Pd catalysts (aged) on (B2) BaMnO 3 -, (B3) La 0.9 MnO 3 -, and (B4) SrMnO 3 -type perovskite-modified alumina supports.
  • FIG. 5b shows perturbated aged TWC light off performance for CO conversions of washcoated (B1) Reference Pd catalyst (aged) on single alumina support, and Pd catalysts (aged) on (B2) BaMnO 3 -, (B3) La 0.9 MnO 3 -, and (B4) SrMnO 3 -type perovskite-modified alumina supports.
  • FIG. 5c shows perturbated aged TWC light off performance for THC conversions of washcoated (B1) Reference Pd catalyst (aged) on single alumina support, and Pd catalysts (aged) on (B2) BaMnO 3 -, (B3) La 0.9 MnO 3 -, and (B4) SrMnO 3 -type perovskite-modified alumina supports.
  • FIG. 6a shows perturbated aged TWC light off performance for NO x conversions of washcoated (B5) reference Rh catalyst (aged) on single alumina support, and Rh catalysts (aged) on (B6) BaMnO 3 -, (B7) La 0.9 MnO 3 -, (B8) La 0.9 Mn 0.7 Zr 0.3 O 3 -, and (B9) La 0.9 Mn 0.9 Zr 0.1 O 3 -type perovskite-modified alumina supports.
  • FIG. 6b shows perturbated aged TWC light off performance for CO conversions of washcoated (B5) reference Rh catalyst (aged) on single alumina support, and Rh catalysts (aged) on (B6) BaMnO 3 -, (B7) La 0.9 MnO 3 -, (B8) La 0.9 Mn 0.7 Zr 0.3 O 3 -, and (B9) La 0.9 Mn 0.9 Zr 0.1 O 3 -type perovskite-modified alumina supports.
  • FIG. 6c shows perturbated aged TWC light off performance for THC conversions of washcoated (B5) reference Rh catalyst (aged) on single alumina support, and Rh catalysts (aged) on (B6) BaMnO 3 -, (B7) La 0.9 MnO 3 -, (B8) La 0.9 Mn 0.7 Zr 0.3 O 3 -, and (B9) La 0.9 Mn 0.9 Zr 0.1 O 3 -type perovskite-modified alumina supports.
  • FIG. 7a shows perturbated aged TWC light off performance for NO x conversions of washcoated (B10) Reference Pd fully formulated catalyst (aged), and Pd catalysts (aged) with (B11) 10% BaMnO 3 -, (B12) 20% BaMnO 3 -, (B13) 20% La 0.9 MnO 3 -, (B14) 10% La 0.9 Mn 0.7 Zr 0.3 O 3 -, (B15) 10% La 0.9 Mn 0.9 Zr 0.1 O 3 -, and (B16) 10% LaFeO 3 -modified alumina- type perovskite-modified alumina supports, and (B17) Reference Pd catalyst with 130 g/ft 3 Pd loading.
  • FIG. 10 washcoated
  • FIG. 7b shows perturbated aged TWC light off performance for CO conversions of washcoated (B10) Reference Pd fully formulated catalyst (aged), and Pd catalysts (aged) with (B11) 10% BaMnO 3 -, (B12) 20% BaMnO 3 -, (B13) 20% La 0.9 MnO 3 -, (B14) 10% La 0.9 Mn 0.7 Zr 0.3 O 3 -, (B15) 10% La 0.9 Mn 0.9 Zr 0.1 O 3 -, and (B16) 10% LaFeO 3 -modified alumina- type perovskite-modified alumina supports, and (B17) Reference Pd catalyst with 130 g/ft 3 Pd loading.
  • FIG. 10 washcoated
  • FIG. 7c shows perturbated aged TWC light off performance for THC conversions of washcoated (B10) Reference Pd fully formulated catalyst (aged), and Pd catalysts (aged) with (B11) 10% BaMnO 3 -, (B12) 20% BaMnO 3 -, (B13) 20% La 0.9 MnO 3 -, (B14) 10% La 0.9 Mn 0.7 Zr 0.3 O 3 -, (B15) 10% La 0.9 Mn 0.9 Zr 0.1 O 3 -, and (B16) 10% LaFeO 3 -modified alumina- type perovskite-modified alumina supports, and (B17) Reference Pd catalyst with 130 g/ft 3 Pd loading.
  • FIG. 10 washcoated
  • FIG. 8a shows perturbated aged TWC light off performance for NO x conversions of washcoated (B18) Reference Rh (aged) fully formulated catalyst, and Rh catalysts (aged) with (B19) 10% La 0.9 MnO 3 -, (B20) 10% La 0.9 Mn 0.7 Zr 0.3 O 3 -, and (B21) 10% La 0.9 Mn 0.9 Zr 0.1 O 3 - modified alumina-type perovskite-modified alumina supports.
  • FIG. 8b shows perturbated aged TWC light off performance for CO conversions of washcoated (B18) Reference Rh (aged) fully formulated catalyst, and Rh catalysts (aged) with (B19) 10% La 0.9 MnO 3 -, (B20) 10% La 0.9 Mn 0.7 Zr 0.3 O 3 -, and (B21) 10% La 0.9 Mn 0.9 Zr 0.1 O 3 - modified alumina-type perovskite-modified alumina supports.
  • FIG. 8c shows perturbated aged TWC light off performance for TWC conversions of washcoated (B18) Reference Rh (aged) fully formulated catalyst, and Rh catalysts (aged) with (B19) 10% La 0.9 MnO 3 -, (B20) 10% La 0.9 Mn 0.7 Zr 0.3 O 3 -, and (B21) 10% La 0.9 Mn 0.9 Zr 0.1 O 3 - modified alumina-type perovskite-modified alumina supports.
  • FIG. 9a shows perturbated aged TWC light off performance for NO x conversions of washcoated (B22) Reference Pt (aged) fully formulated catalyst, and Pt catalysts (aged) with (B23) 10% BaMnO 3 -, (B24) 20% BaMnO 3 -, (B25) 10% La 0.9 MnO 3 -, (B26) 20% La 0.9 MnO 3 -, (B27) 10% CaMnO 3 -, (B28) 20% CaMnO 3 -, and (B29) 10% LaFeO 3 -modified alumina supports.
  • FIG. 9b shows perturbated aged TWC light off performance for CO conversions of washcoated (B22) Reference Pt (aged) fully formulated catalyst, and Pt catalysts (aged) with (B23) 10% BaMnO 3 -, (B24) 20% BaMnO 3 -, (B25) 10% La 0.9 MnO 3 -, (B26) 20% La 0.9 MnO 3 -, (B27) 10% CaMnO 3 -, (B28) 20% CaMnO 3 -, and (B29) 10% LaFeO 3- modified alumina supports.
  • FIG. 10 shows perturbated aged TWC light off performance for THC conversions of washcoated (B22) Reference Pt (aged) fully formulated catalyst, and Pt catalysts (aged) with (B23) 10% BaMnO 3 -, (B24) 20% BaMnO 3 -, (B25) 10% La 0.9 MnO 3 -, (B26) 20% La 0.9 MnO 3 -, (B27) 10% CaMnO 3 -, (B28) 20% CaMnO 3 -, and (B29) 10% LaFeO 3 -modified alumina supports.
  • FIG. 10 shows cumulative NO x emission during vehicle test of aged (B30) Reference PdRh fully formulated catalysts vs.
  • PdRh catalysts (aged) with (B31) 10% BaMnO 3 (IWI)-, (B32) 10% BaMnO 3 (SD)-, and (B33) 20% BaMnO 3 (IWI)-modified alumina.
  • B31 10% BaMnO 3 (IWI)-
  • B32 10% BaMnO 3 (SD)-
  • B33 20% BaMnO 3 (IWI)-modified alumina.
  • the present invention provides a composition comprising alumina, the alumina being surface-modified with a perovskite type compound of formula (I); wherein formula (I) is defined by A x-y A’ y B 1-z B’ z O 3 ; where: A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb, V, W, Bi, Zn, Sn, Pt, Rh, Pd, Ru, Au, Ag, and Ir;
  • Alumina is a “classical” support materials used in emission treatment catalysts, such as TWCs. Alumina is known to provide high surface area for active PGM metals and promoter species. It is also more thermally robust than other mixed oxide support toward harsh TWC operation conditions.
  • the inventors of the present invention have found that surface-modifying such an alumina support with a perovskite-type compound can impart OSC properties to the alumina, which would otherwise have minimal OSC properties, while still being able to retain most of its surface area at thermal ageing conditions. This may advantageously also facilitate improved promotion of supported PGM species supported on the modified support (the composition of the invention), if present, in order to obtain improved TWC conversions.
  • surface-modified as used herein may encompass that the perovskite type compound is supported or coated on the alumina, for example.
  • the perovskite type compound is physically and/or chemically attached to or supported on the surface of the alumina, preferably in a (highly) dispersed form.
  • surface-modified does not encompass merely a physical blend or mixture of the bulk perovskite type compound and alumina.
  • the perovskite type compound is not in bulk form in this sense. For example, under extreme oxidising and/or ageing conditions, it is thought that an aluminate may form between the perovskite type compound and the alumina to help bond the perovskite type compound to the surface of the alumina.
  • an aluminate may be situated between the alumina and the perovskite type compound, such as at the interface between the alumina and the perovskite type compound.
  • the term “surface-modified” as used herein may also encompass that the perovskite type compound has smaller particle sizes than the alumina.
  • the term “surface- modified” as used herein may also encompass that the alumina is in bulk form, and the perovskite type compound is dispersed on the surface and/or within the pores of the bulk alumina.
  • the perovskite compound may be stabilised by the alumina.
  • the drawbacks of bulk perovskite type compounds such as their low surface-area-to-volume ratio and their lack of stability at exhaust gas catalyst operating temperatures, may be mitigated, while imparting their advantageous OSC properties to the alumina support. That is, the alumina phase may act both as a support to provide high surface area and to stabilize the perovskite nanocrystalline phase (e.g. from sintering) at thermal ageing conditions.
  • Synergistic interactions between the dispersed perovskites and the supporting species may also occur, which may lead to enhanced TWC performance.
  • the perovskite itself may also exhibit intrinsic activity for TWC reactions, facilitating the PGM performance, which may allow for potential reduction of PGM loading.
  • Such advantages may not be realized by the use of bulk-phase perovskite type compounds in catalysts for treating exhaust gas, particularly TWC catalysts.
  • the composition of the invention may be used in place of existing support materials, such as where alumina is used as a support material in a known catalyst article, to provide OSC properties to the catalyst, or even to replace existing OSC support materials, such as ceria-zirconia support materials, which may lead to further and/or improved OSC properties.
  • existing support materials such as where alumina is used as a support material in a known catalyst article
  • OSC support materials such as ceria-zirconia support materials
  • replacing conventional support materials with the composition of the invention can significantly decrease the T50 (the temperature at which 50% conversion is reached) of conversion for NO x , CO and/or THC (total hydrocarbon) abatement.
  • perovskite as used herein takes on its usual meaning in the art, i.e. a perovskite type compound may refer to the class of compounds which have a similar or distorted type of crystal structure to CaTiO 3 .
  • composition and/or perovskite type compound of formula (I) may comprise inevitable impurities, typically less than 1 wt.%, preferably less than 0.5 wt.%, more preferably less than 0.1 wt.%.
  • the composition consists of alumina, the alumina being surface-modified with a perovskite type compound of formula (I).
  • a and/or A’ is an ion of a metal selected from the group consisting of Ca, Mg, Ba, Ca, Y, La, Sr, Nd, Ce and Gd, more preferably A and/or A’ is an ion of a metal selected from the group consisting of Ca, Ba, La and Sr.
  • B and/or B’ is an ion of a metal selected from the group consisting of Mn, Co, Fe, Zr and Ni, more preferably, B and/or B’ is an ion of a metal selected from the group consisting of Mn, Zr, and Fe.
  • B and/or B’ is doped with PGM elements comprising one or more of Pt, Pd and Rh, i.e. B and/or B’ may further comprise, in addition to the preferred metals listed above, an ion of a metal selected from the group consisting of Pt, Pd and Rh.
  • Such compositions may be particularly suitable for use in the applications described herein, for example in a TWC.
  • x is from 0.8 to 1, more preferably from 0.9 to 1 or alternatively, but still preferred, from 0.7 to 0.9, more preferably from 0.8 to 0.9.
  • y is from 0 to 0.3, more preferably from 0 to 0.2, more preferably from greater than 0 to 0.2.
  • z is from 0 to 0.4, more preferably from 0 to 0.3, still more preferably from greater than 0 to 0.2.
  • Such compositions may be particularly suitable for use in the applications described herein, for example in a TWC.
  • Such compositions may be particularly suitable for use in the applications described herein, for example in a TWC.
  • z is 0.
  • y is 0.
  • z can be 0 when y > 0 and y can be 0 when z > 0.
  • A is La and B is Mn.
  • B Mn.
  • compositions may be particularly suitable for use in the applications described herein, for example in a TWC.
  • x is 1.
  • the alumina comprises gamma alumina.
  • Gamma alumina is known in the art. More preferably, the alumina consists of gamma alumina.
  • the alumina comprises theta alumina. Theta alumina is known in the art.
  • the alumina consists of theta alumina.
  • the alumina comprises, or consists of, gamma alumina and/or theta alumina.
  • the alumina is doped. Suitable dopants are known in the art.
  • the alumina is doped with an oxide of one or more of La, Ba, Sr, Mg, Mn, Y, Nd, Pr, Ce, Zr, Ti, Fe, Cu, Co, Zn, Si, and Ni, more preferably La, or La and Mg.
  • Such doped alumina may be particularly effective as a support material.
  • the dopant is present in the alumina in an amount of from 0.001 wt.% to 20 wt.%, and more preferably from 0.5 wt.% to 10 wt.%, based on the total weight of alumina.
  • the composition comprises from 1 to 50 wt.% of the perovskite type compound, based on the total weight of the perovskite type compound and the alumina, preferably from 5 to 30 wt.%, more preferably from 5 to 25 wt.%, still more preferably from 10 to 20 wt.%.
  • the perovskite type compound may be highly dispersed on the alumina, for example.
  • Such a ratio of perovskite type compound may provide a particularly stable composition having improved OSC properties.
  • the alumina is further surface-modified with a mixed oxide composite of formula (I). This may occur, for example, when phases other than the perovskite phase of formula (I) are present, such as due to incomplete formation of the perovskite phase during synthesis or formation of an aluminate at the boundary between the perovskite type compound and the alumina.
  • the present invention provides a method of manufacturing a composition comprising alumina, the alumina being surface-modified with a perovskite type compound of formula (I); wherein formula (I) is defined by A x-y A’ y B 1-z B’ z O 3 ; where: A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb, V, W, Bi, Zn, Sn, Pt, Rh, Pd, Ru, Au, Ag
  • Such a method may be considered as a (modified) Pechini method.
  • the term “slurry” as used herein may encompass a liquid comprising insoluble material, e.g. insoluble particles.
  • the slurry is typically stirred, more typically for at least 10 minutes, more typically for at least 30 minutes, even more typically for at least an hour.
  • Increased contacting and/or stirring times may increase the dispersion of the perovskite type compound on the alumina.
  • Contacting the solution with alumina may typically comprise adding alumina, for example in powder form, to the solution.
  • contacting the solution with alumina may comprise combining the solution with a slurry comprising alumina, for example alumina powder in water.
  • the contacting step is not particularly limited in this regard.
  • the solution further comprises an organic solvent, preferably ethylene glycol.
  • the solution does not comprise an inorganic solvent, i.e. the solution is preferably an aqueous solution.
  • the one or more salts preferably comprise acetate, nitrate, oxynitrate, chloride, ammonium nitrate, hydroxide, oxalate and/or citrate salts, more preferably acetate, nitrate and/or oxynitrate salts.
  • heating the slurry comprises a first step of heating the slurry to a temperature of from 150 to 350 °C to form a gel.
  • heating the slurry comprises a first step of heating the slurry to a temperature of from 200 to 300°C, such as from 250 to 300°C to form a gel.
  • heating the slurry comprises calcination, preferably after the heating step described above (i.e.
  • calcination comprising a first step of heating the slurry to a temperature of from 150 to 350 °C to form a gel.
  • the term “calcination” as used herein may encompass a thermal treatment process in the absence of, or limited supply of, air or oxygen to bring about a thermal decomposition or change. However, typically, calcination in the present context involves heating in air in an oven. Preferably, the calcination comprises heating at a temperature of from 300 to 500 °C, preferably form 350 to 450 °C, for from 1 to 10 hours, preferably from 3 to 6 hours.
  • the calcination comprises heating at a temperature of from 600 to 1000 °C, preferably from 700 to 900 °C for from 1 to 8 hours, preferably from 2 to 5 hours. More preferably, the calcination comprises a first calcination step comprising heating at a temperature of from 300 to 500 °C, preferably from 350 to 450 °C, for from 1 to 10 hours, preferably from 3 to 6 hours, followed by a second calcination step comprising heating at a temperature of from 600 to 1000 °C, preferably from 700 to 900 °C, for from 1 to 8 hours, preferably from 2 to 5 hours.
  • the first, lower temperature, calcination step may facilitate the formation of a mixed oxide of the perovskite-precursor metals, i.e. forming a mixed oxide from the precursor salts
  • the second, higher temperature, calcination step may then facilitate the formation of a dense perovskite structure supported on the alumina (i.e. a surface-modified alumina).
  • the perovskite type compound is not in bulk form, but is supported on the surface of the alumina.
  • the organic acid comprises a carboxylic acid, more preferably a di- or tri- carboxylic acid.
  • the organic acid preferably comprises, or even consists of, citric acid, tannic acid, humic acid, succinic acid, EDTA, DTPA and/or other chelating agents, more preferably citric acid, tannic acid, humic acid, succinic acid, EDTA and/or DTPA, even more preferably citric acid.
  • the composition manufactured by the method of this aspect is the composition of the first aspect described herein.
  • the present invention provides a composition obtained or obtainable by the method of the above aspect.
  • the inventors of the present invention have found that providing such a composition by surface-modifying an alumina support with a perovskite-type compound can impart OSC properties to the alumina, which would otherwise have minimal OSC properties, while still being able to retain most of its surface area at thermal ageing conditions. This may advantageously also facilitate improved promotion of supported PGM species supported on the modified support (the composition of the invention), if present, in order to obtain improved TWC conversions.
  • the perovskite compound may be stabilised by the alumina.
  • the drawbacks of bulk perovskite type compounds such as their low surface-area-to-volume ratio and their lack of stability at exhaust gas catalyst operating temperatures, may be mitigated, while imparting their advantageous OSC properties to the alumina support. That is, the alumina phase may act both as a support to provide high surface area and to stabilize the perovskite nanocrystalline phase (e.g. from sintering) at thermal ageing conditions. Synergistic interactions between the dispersed perovskites and the supporting species (e.g. PGM and promoter) may also occur, which may lead to enhanced TWC performance. Besides the promotional effect, the perovskite itself may also exhibit intrinsic activity for TWC reactions, facilitating the PGM performance, which may allow for potential reduction of PGM loading.
  • the supporting species e.g. PGM and promoter
  • the composition of the invention may be used in place of existing support materials, such as where alumina is used as a support material in a known catalyst article, to provide OSC properties to the catalyst, or even to replace existing OSC support materials, such as ceria-zirconia support materials, which may lead to further and/or improved OSC properties.
  • the present inventors have surprisingly been able to utilise the OSC benefits of perovskite type compounds for use in emission treatment catalysts, while at least partially mitigating the drawbacks and instability of such compounds in bulk form at the operating temperatures of the catalysts, e.g. TWCs.
  • the same advantages as for the composition of the first aspect apply to the composition of this aspect.
  • the present invention provides a method of manufacturing a composition comprising alumina, the alumina being surface-modified with a perovskite type compound of formula (I); wherein formula (I) is defined by A x-y A’ y B 1-z B’ z O 3 ; where: A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb, V, W, Bi, Zn, Sn, Pt, Rh, Pd, Ru, Au, Ag
  • IW or IWI Incipient wetness impregnation
  • IW or IWI is a well-known technique in the field. The skilled person would be able to perform an appropriate incipient wetness impregnation method without further direction.
  • Contacting alumina with A, B, and optionally A’ and/or B’ using one or more salts of A, one or more salts of B and optionally one or more salts of A’ and/or one or more salts of B’ via incipient wetness impregnation may comprise impregnating alumina with A, B, and optionally A’ and/or B’ using one or more salts of A, one or more salts of B and optionally one or more salts of A’ and/or one or more salts of B’ via incipient wetness impregnation, for example.
  • the one or more salts preferably comprise acetate, nitrate, oxynitrate, chloride, ammonium nitrate, hydroxide, oxalate and/or citrate salts, more preferably acetate, nitrate and/or oxynitrate salts.
  • heating the impregnated alumina comprises a first step of drying the impregnated alumina at a temperature of from 50 to 150 °C, preferably from 50 to 100 °C for from 1 hour to 24 hours, preferably 6 hours to 12 hours.
  • heating the impregnated alumina comprises calcination, preferably after the heating step described above (i.e.
  • the calcination comprises heating at a temperature of from 300 to 500 °C, preferably from 350 to 450 °C, for from 1 to 10 hours, preferably from 3 to 6 hours.
  • the calcination comprises heating at a temperature of from 600 to 1000 °C, preferably from 700 to 900 °C for from 1 to 8 hours, preferably from 2 to 5 hours.
  • the calcination comprises a first calcination step comprising heating at a temperature of from 300 to 500 °C, preferably from 350 to 450 °C, for from 1 to 10 hours, preferably from 3 to 6 hours, followed by a second calcination step comprising heating at a temperature of from 600 to 1000 °C, preferably from 700 to 900 °C, for from 1 to 8 hours, preferably from 2 to 5 hours.
  • a first, lower temperature, calcination step may facilitate the formation of a mixed oxide of the perovskite-precursor metals, i.e.
  • the composition manufactured by the method of this aspect is the composition of the first aspect described herein.
  • the present invention provides a composition obtained or obtainable by the method of the above aspect.
  • the inventors of the present invention have found that providing such a composition by surface-modifying an alumina support with a perovskite-type compound can impart OSC properties to the alumina, which would otherwise have minimal OSC properties, while still being able to retain most of its surface area at thermal ageing conditions. This may advantageously also facilitate improved promotion of supported PGM species supported on the modified support (the composition of the invention), if present, in order to obtain improved TWC conversions.
  • the perovskite compound may be stabilised by the alumina.
  • the drawbacks of bulk perovskite type compounds such as their low surface-area-to-volume ratio and their lack of stability at exhaust gas catalyst operating temperatures, may be mitigated, while imparting their advantageous OSC properties to the alumina support. That is, the alumina phase may act both as a support to provide high surface area and to stabilize the perovskite nanocrystalline phase (e.g. from sintering) at thermal ageing conditions. Synergistic interactions between the dispersed perovskites and the supporting species (e.g. PGM and promoter) may also occur, which may lead to enhanced TWC performance. Besides the promotional effect, the perovskite itself may also exhibit intrinsic activity for TWC reactions, facilitating the PGM performance, which may allow for potential reduction of PGM loading.
  • the supporting species e.g. PGM and promoter
  • the composition of the invention may be used in place of existing support materials, such as where alumina is used as a support material in a known catalyst article, to provide OSC properties to the catalyst, or even to replace existing OSC support materials, such as ceria-zirconia support materials, which may lead to further and/or improved OSC properties.
  • the present inventors have surprisingly been able to utilise the OSC benefits of perovskite type compounds for use in emission treatment catalysts, while at least partially mitigating the drawbacks and instability of such compounds in bulk form at the operating temperatures of the catalysts, e.g. TWCs.
  • the same advantages as for the composition of the first aspect apply to the composition of this aspect.
  • the present invention provides a method of manufacturing a composition comprising alumina, the alumina being surface-modified with a perovskite type compound of formula (I); wherein formula (I) is defined by A x-y A’ y B 1-z B’ z O 3 ; where: A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb, V, W, Bi, Zn, Sn, Pt, Rh, Pd, Ru, Au, Ag
  • Spray drying is a well-known technique in the field. The skilled person would be able to perform an appropriate spray drying method without further direction.
  • Contacting the solution with alumina may typically comprise adding alumina, for example in powder form, to the solution. However, contacting the solution with alumina may comprise combining the solution with a slurry comprising alumina, for example alumina powder in water. The contacting step is not particularly limited in this regard.
  • the one or more salts preferably comprise acetate, nitrate, oxynitrate, chloride, ammonium nitrate, hydroxide, oxalate and/or citrate salts, more preferably acetate, nitrate and/or oxynitrate salts.
  • the solution is an aqueous solution.
  • heating the spray-dried powder comprises calcination.
  • the calcination comprises heating at a temperature of from 300 to 500°C, preferably from 350 to 450 °C, for from 1 to 10 hours, preferably from 3 to 6 hours.
  • the calcination comprises heating at a temperature of from 600 to 1000 °C, preferably from 700 to 900 °C for from 1 to 8 hours, preferably from 2 to 5 hours.
  • the calcination comprises a first calcination step comprising heating at a temperature of from 300 to 500 °C, preferably from 350 to 450 °C, for from 1 to 10 hours, preferably from 3 to 6 hours, followed by a second calcination step comprising heating at a temperature of from 600 to 1000 °C, preferably from 700 to 900 °C, for from 1 to 8 hours, preferably from 2 to 5 hours.
  • a first, lower temperature, calcination step may facilitate the formation of a mixed oxide of the perovskite-precursor metals, i.e.
  • the inlet temperature of the spray drying is from 100 to 300 °C, more preferably from 150 to 250 °C.
  • the inlet temperature is a well-known term within the field of spray drying.
  • the composition manufactured by the method of this aspect is the composition of the first aspect described herein.
  • the present invention provides a composition obtained or obtainable by the method of the above aspect.
  • the inventors of the present invention have found that providing such a composition by surface-modifying an alumina support with a perovskite-type compound can impart OSC properties to the alumina, which would otherwise have minimal OSC properties, while still being able to retain most of its surface area at thermal ageing conditions. This may advantageously also facilitate improved promotion of supported PGM species supported on the modified support (the composition of the invention), if present, in order to obtain improved TWC conversions.
  • the perovskite compound may be stabilised by the alumina.
  • the drawbacks of bulk perovskite type compounds such as their low surface-area-to-volume ratio and their lack of stability at exhaust gas catalyst operating temperatures, may be mitigated, while imparting their advantageous OSC properties to the alumina support. That is, the alumina phase may act both as a support to provide high surface area and to stabilize the perovskite nanocrystalline phase (e.g. from sintering) at thermal ageing conditions. Synergistic interactions between the dispersed perovskites and the supporting species (e.g. PGM and promoter) may also occur, which may lead to enhanced TWC performance. Besides the promotional effect, the perovskite itself may also exhibit intrinsic activity for TWC reactions, facilitating the PGM performance, which may allow for potential reduction of PGM loading.
  • the supporting species e.g. PGM and promoter
  • the composition of the invention may be used in place of existing support materials, such as where alumina is used as a support material in a known catalyst article, to provide OSC properties to the catalyst, or even to replace existing OSC support materials, such as ceria-zirconia support materials, which may lead to further and/or improved OSC properties.
  • the present inventors have surprisingly been able to utilise the OSC benefits of perovskite type compounds for use in emission treatment catalysts, while at least partially mitigating the drawbacks and instability of such compounds in bulk form at the operating temperatures of the catalysts, e.g. TWCs.
  • the same advantages as for the composition of the first aspect apply to the composition of this aspect.
  • the present invention provides a method of manufacturing a composition comprising alumina, the alumina being surface-modified with a perovskite type compound of formula (I); wherein formula (I) is defined by A x-y A’ y B 1-z B’ z O 3 ; where: A is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; A’ is an ion of a metal selected from the group consisting of Li, Na, K, Cs, Mg, Sr, Ba, Ca, Y, La, Ce, Pr, Nd, and Gd; B is an ion of a metal selected from the group consisting of Cu, Mn, Mo, Co, Fe, Ni, Cr, Ti, Zr, Al, Ga, Sc, Nb, V, W, Bi, Zn, Sn, Pt, Rh, Pd, Ru, Au, Ag
  • Contacting the solution with alumina may typically comprise adding alumina, for example in powder form, to the solution.
  • contacting the solution with alumina may comprise combining the solution with a slurry comprising alumina, for example alumina powder in water.
  • the contacting step is not particularly limited in this regard.
  • the one or more salts preferably comprise acetate, nitrate, oxynitrate, chloride, ammonium nitrate, hydroxide, oxalate and/or citrate salts, more preferably acetate, nitrate and/or oxynitrate salts.
  • the method comprises contacting the slurry with a base.
  • contacting the slurry with a base comprises contacting the slurry with a solution comprising the base, preferably an aqueous solution comprising the base.
  • a solution comprising the base preferably an aqueous solution comprising the base.
  • the method may further comprise filtering and/or washing the alumina after addition of the base (i.e. with the precipitated content thereon) and prior to heating the solid residue. Recovering a solid residue from the slurry may encompass filtering the slurry to obtain a solid residue.
  • solid residue may encompass a filter cake, for example. Such a filter cake is well known in the art.
  • the calcination comprises heating at a temperature of from 300 to 500 °C, preferably from 350 to 450 °C, for from 1 to 10 hours, preferably from 3 to 6 hours.
  • the calcination comprises heating at a temperature of from 600 to 1000 °C, preferably from 700 to 900 °C for from 1 to 8 hours, preferably from 2 to 5 hours.
  • the calcination comprises a first calcination step comprising heating at a temperature of from 300 to 500 °C, preferably from 350 to 450 °C, for from 1 to 10 hours, preferably from 3 to 6 hours, followed by a second calcination step comprising heating at a temperature of from 600 to 1000 °C, preferably from 700 to 900 °C, for from 1 to 8 hours, preferably from 2 to 5 hours.
  • a first, lower temperature, calcination step may facilitate the formation of a mixed oxide of the perovskite-precursor metals, i.e.
  • the second, higher temperature, calcination step may then facilitate the formation of a dense perovskite structure supported on the alumina (i.e. a surface-modified alumina).
  • the perovskite type compound is not in bulk form, but may be supported on the surface of the alumina in a dispersed state.
  • the base comprises ammonium hydroxide.
  • recovering a solid residue from the slurry comprises filtering the slurry to obtain a solid residue and washing the solid residue with water, preferably excess water.
  • the composition manufactured by the method of this aspect is the composition of the first aspect described herein.
  • the present invention provides a composition obtained or obtainable by the method of the above aspect.
  • the inventors of the present invention have found that providing such a composition by surface-modifying an alumina support with a perovskite-type compound can impart OSC properties to the alumina, which would otherwise have minimal OSC properties, while still being able to retain most of its surface area at thermal ageing conditions. This may advantageously also facilitate improved promotion of supported PGM species supported on the modified support (the composition of the invention), if present, in order to obtain improved TWC conversions.
  • the perovskite compound may be stabilised by the alumina.
  • the drawbacks of bulk perovskite type compounds such as their low surface-area-to-volume ratio and their lack of stability at exhaust gas catalyst operating temperatures, may be mitigated, while imparting their advantageous OSC properties to the alumina support. That is, the alumina phase may act both as a support to provide high surface area and to stabilize the perovskite nanocrystalline phase (e.g. from sintering) at thermal ageing conditions.
  • Synergistic interactions between the dispersed perovskites and the supporting species may also occur, which may lead to enhanced TWC performance.
  • the perovskite itself may also exhibit intrinsic activity for TWC reactions, facilitating the PGM performance, which may allow for potential reduction of PGM loading.
  • Such advantages may not be realized by the use of bulk-phase perovskite type compounds in catalysts for treating exhaust gas, particularly TWC catalysts.
  • the composition of the invention may be used in place of existing support materials, such as where alumina is used as a support material in a known catalyst article, to provide OSC properties to the catalyst, or even to replace existing OSC support materials, such as ceria-zirconia support materials, which may lead to further and/or improved OSC properties.
  • existing support materials such as where alumina is used as a support material in a known catalyst article
  • OSC support materials such as ceria-zirconia support materials
  • replacing conventional support materials with the composition of the invention can significantly decrease the T50 (the temperature at which 50% conversion is reached) of conversion for NO x , CO and/or THC (total hydrocarbon) abatement.
  • the present inventors have surprisingly been able to utilise the OSC benefits of perovskite type compounds for use in emission treatment catalysts, while at least partially mitigating the drawbacks and instability of such compounds in bulk form at the operating temperatures of the catalysts, e.g. TWCs.
  • the same advantages as for the composition of the first aspect apply to the composition of this aspect.
  • the present invention provides a catalyst article comprising a substrate, the substrate having the composition described herein disposed thereon.
  • the term “catalyst article” used herein may encompass an article in which a catalyst is supported thereon or therein.
  • the article may take the form of, for example, a honeycomb monolith, or a filter, e.g.
  • substrate as used herein may encompass, for example, a ceramic or metallic honeycomb, or a filter block, e.g. a wall flow filter or flow-through filter.
  • the substrate may comprise a ceramic monolithic substrate.
  • the substrate may vary in its material composition, size and configuration, cell shape and density, and wall thickness. Suitable substrates are known in the art.
  • disposed thereon in the context of this aspect may encompass both having the composition directly disposed on the substrate, i.e. with no intervening material, and/or indirectly disposed on the substrate, i.e. with intervening material.
  • the term “disposed thereon” may also encompass having the composition disposed therein, for example within the pores of the substrate, i.e. wherein the composition is disposed thereon and/or therein.
  • the composition described herein may be incorporated into one or more washcoat regions, zones or layers disposed in any order on the substrate.
  • Such substrate-washcoat formulations are well-known in the field.
  • the term “washcoat” as used herein is well-known in the field and refers to an adherent coating that is applied to a substrate usually during the production of a catalyst.
  • the catalyst article is for treating exhaust gas.
  • the catalyst article comprises a three-way catalyst (TWC), more preferably the catalyst article is a TWC.
  • a platinum group metal is supported on the composition.
  • the PGM may be supported on the surface and/or within the pores of the alumina.
  • the PGM may also be supported on the perovskite type compound.
  • the PGM may be located at a boundary between the alumina and the perovskite type compound supported thereon. Without wishing to be bound by theory, it is thought that the presence of the perovskite type compound may further promote the catalytic activity of the PGM as well as increasing the resistance of the PGM nanoparticles to sintering. PGM sintering may lower the catalytic activity of the PGM.
  • PGM as used herein encompasses one or more platinum group metals selected from ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • the PGM comprises Pt, Pd, Rh, or a mixture or alloy thereof. Such metals may be particularly suitable for carrying out three-way catalysis.
  • the PGM may be in the form of an alloy.
  • the catalyst article is for use in an emission treatment system.
  • the catalyst article is for three-way catalysis.
  • the catalyst article has a washcoat loading of from 1 g/in 3 to 3 g/in 3 .
  • the substrate comprises a wall flow filter substrate.
  • the substrate comprises a flow-through substrate.
  • the catalyst article comprises a bottom layer of support material having rhodium thereon and a top layer of support material having palladium thereon.
  • the catalyst article comprises a bottom layer of support material having palladium thereon and a top layer of support material having rhodium thereon.
  • the support material may comprise any suitable known support material.
  • the support material comprises the composition described herein. That is, the support material present in the bottom layer and/or the top layer may comprise the composition described herein.
  • the catalyst article preferably comprises from 2 g/ft 3 to 15 g/ft 3 rhodium, more preferably from 3 g/ft 3 to 10 g/ft 3 rhodium.
  • the catalyst article preferably comprises from 20 g/ft 3 to 200 g/ft 3 palladium, more preferably from 30 g/ft 3 to 150 g/ft 3 palladium.
  • the catalyst article preferably comprises from 2 g/ft 3 to 200 g/ft 3 platinum, preferably from 10 g/ft 3 to 100 g/ft 3 platinum.
  • the present invention provides an emission treatment system comprising the catalyst article described herein.
  • the emission treatment system is for a gasoline engine.
  • the gasoline engine operates under stoichiometric conditions.
  • the present invention provides a method of treating an exhaust gas, the method comprising: providing the catalyst article described herein; and contacting the catalyst article with an exhaust gas.
  • the exhaust gas is from a gasoline engine.
  • the gasoline engine operates under stoichiometric conditions.
  • a slurry was prepared with DI water, and appropriate amount of binder and thickening agent for a final batch solid of 22%. The slurry was mixed vigorously with VWR vortex mixer until homogeneous. 4. 1 x 3 inch ceramic substrate cores were coated targeting 1.2 inch dose from the inlet end, then dried with air cure. 5. The brick was fired at 500 °C for 30 min in a static oven.
  • Example B2 3 wt% Pd/10% BMO modified alumina washcoated catalyst 1. 3 wt% Pd (as Palladium nitrate solution) was impregnated on 10% BaMnO 3 modified alumina powder (Example A1) using incipient wetness impregnation. 2.
  • Reference Example B10 Fully formulated single layer Pd washcoat 1.
  • a solution was prepared with the required amount of Pd nitrate (with Pd loading 100 g/ft 3 ). 2.
  • Added were 1 g/in 3 of stabilized alumina powder, and 1 g/in 3 of CZO material, before mixing for 1 hr. 3.
  • Added was 300 g/ft 3 of Barium sulfate, before mixing for at least 1 hr. 4.
  • Added was an appropriate amount of binder before mixing for 1 hr. 5.
  • Solids were adjusted to 30%, thickening agent was added and before mixing overnight. 6. 50-55% from the inlet end of a 1 x 3 inch ceramic substrate core was coated, dried with air cure, then coated 50-55% dose length from the outlet end. 7.
  • Example B11 Fully formulated single layer Pd washcoat with 10%BMO modified alumina 1.
  • a solution was prepared with the required amount of Pd nitrate (with Pd loading 100 g/ft 3 ). 2.
  • Added was 1 g/in 3 of 10% BaMnO 3 modified alumina powder (Example A3), and 1 g/in 3 of CZO material, before mixing for 1 hr. 3.
  • Added was 300 g/ft 3 of Barium sulfate, before mixing for at least 1 hr. 4.
  • Added was an appropriate amount of binder before mixing for 1 hr. 5. Solids were adjusted to 30%, thickening agent was added before mixing overnight. 6.
  • Examples B12-B17 Catalyst preparation procedures for Examples B12-B17 are similar to Examples B10 and B11, with Pd loading and type of modified alumina listed in the following Table 3. Table 3. Pd loading and types of modified alumina for Examples B12- B17 Reference Example B18: Fully formulated single layer Rh washcoat 1. A solution was prepared with the required amount of Rh nitrate (with Rh loading 4.8 g/ft 3 ). 2.
  • a slurry of unmilled stabilized alumina (0.5 g/in 3 ) was prepared, and mixed until homogeneous (at least 30 min). 3. Ammonium was added dropwise until pH 7.0-7.5 was reached. 4. The slurry was mixed for 1 hr so the Rhodium was precipitated throughout the washcoat. 5. Added was milled stabilized alumina (0.1 g/in 3 ) and CZO (0.7 g/in 3 ) before mixing for 30 minutes until homogeneous. 6. An appropriate amount of binder was added before mixing for 30 minutes, and solids were adjusted to 23%. 7. Added was thickening agent targeting ⁇ 1.0-1.2 wt% water based, before mixing overnight. 8.
  • Example B19 Fully formulated single layer Rh washcoat with 10%LMO modified alumina 1. A solution was prepared with the required amount of Rh nitrate (with Rh loading 4.8 g/ft 3 ). 2. A slurry of unmilled 10% La 0.9 MnO 3 modified alumina was prepared (Example A9, 0.5 g/in 3 ), and mixed until homogeneous (at least 30 min). 3. Ammonium was added dropwise until pH 7.0-7.5 was reached. 4.
  • the slurry was mixed for 1 hr so the Rhodium precipitated throughout the washcoat. 5. Added was milled stabilized alumina (0.1 g/in 3 ) and CZO (0.7 g/in 3 ) before mixing for 30 minutes until homogeneous. 6. An appropriate amount of binder was added before mixing for 30 minutes, and solids were adjusted to 23%. 7. Added was thickening agent targeting ⁇ 1.0-1.2 wt% water based, before mixing overnight. 8. 50-55% from the inlet end of a 1 x 3 inch ceramic substrate core was coated, dried with air cure, then 50-55% dose length from the outlet end was coated. 9. The brick was fired at 500 °C for 30 min in a static oven.
  • Examples B20 and B21 Catalyst preparation procedures for Examples B20 and B21 are similar to Examples B18 and B19, with Rh loading and type of modified alumina listed in the following Table 4. Table 4. Rh loading and types of modified alumina for Examples B20 and B21 Reference Example B22: Fully formulated single layer Pt washcoat 1. A solution was prepared with the required amount of Pt nitrate (with Pt loading 20 g/ft 3 ). 2. Stabilized alumina (1 g/in 3 ) and CZO (1 g/in 3 ) were added to the batch. 3. pH was adjusted to 5-6.6 with ammonia, and mixed for at least 1 hour. 4. Solids were adjusted to target (suggest ⁇ 30%). 5. An appropriate amount of thickening agent was added before mixing overnight.
  • Example B23 Fully formulated single layer Pt washcoat with 10%BMO modified alumina 1. A solution was prepared with the required amount of Pt nitrate (with Pt loading 20 g/ft 3 ). 2. 10% BaMnO 3 modified alumina (A3, 1 g/in 3 ) and CZO (1 g/in 3 ) were added to the batch. 3. pH was adjusted to 5-6.6 with ammonia, and mixed for at least 1 hour. 4. Solids were adjusted to target (suggest ⁇ 30%). 5. An appropriate amount of thickening agent was added before overnight. 6.
  • Examples B24-B29 Catalyst preparation procedures for Examples B24-B29 are similar to Examples B22 and B23, with Pt loading and type of modified alumina listed in the following Table 5. Table 5. Pt loading and types of modified alumina for Examples B24-B29 Reference Example B30: Fully formulated double layer PdRh washcoat Bottom layer: 1. A solution of the required amount of Pd nitrate (with Pd loading 80 g/ft 3 ) was preapred. 2.
  • a solution of the required amount of Rh nitrate (with Rh loading 3.8 g/ft 3 ) was prepared. 2.
  • a slurry of milled stabilized alumina (0.8 g/in 3 ) was added, before mixing for at least 1 hr. 3.
  • NH4OH was added to a pH of 6-7 and mixed for at least 1 hr. 4.
  • a slurry of milled CZO (0.8 g/in 3 ) was added, before mixing for at least 1 hr. 5.
  • Thickening agent was added and stirred overnight 6. 50-55% from the inlet end of a 1 x 3 inch ceramic substrate core was coated, dried with air cure, then 50-55% dose length from the outlet end was coated. 7.
  • FIG.1 shows a powder XRD pattern of 20% BaMnO 3 modified alumina according the Example A6. A hexagonal polytype of the BaMnO 3 perovskite structure was detected.
  • FIG. 2 and FIG. 3 respectively, show the selected STEM elemental mapping and images of (A11) 20% La 0.9 MnO 3 modified alumina and (A6) 20% BaMnO 3 modified alumina. Universal dispersion of perovskite A site and B site elements on alumina support were observed with both samples. High resolution STEM images also showed lattice spacings at particle surfaces/edges, suggesting formation or ordered crystallite structures on the alumina support.
  • OSC of selected perovskite-modified alumina samples The alumina support originally exhibits no OSC property. After surface modification with the perovskite phases, pronounced OSC function is introduced to the alumina support.
  • OSC measurement a powder sample was pre-oxidized at each temperature, and CO was subsequently flowed through the sample, when CO was converted to CO 2 by the oxygen species donated from the powder sample. The total OSC of the solid sample is therefore corresponds to the amount of CO 2 produced per gram of sample.
  • FIG. 5a, FIG. 5b and FIG. 5c respectively, show TWC light off performance (NO x conversion, CO conversion and THC conversion) of single alumina or modified alumina supported Pd catalysts.
  • the figures show perturbated aged TWC light off performance for (a) NO, (b) CO, and (c) THC conversions of washcoated (B1) Reference Pd catalyst (aged) on single alumina support, and Pd catalysts (aged) on (B2) BaMnO 3 -, (B3) La 0.9 MnO 3 -, and (B4) SrMnO 3 -type perovskite-modified alumina support.
  • the modified supports were synthesized via Pechini method.
  • FIG. 6a, FIG. 6b and FIG. 6c show TWC light off performance (NO x conversion, CO conversion and THC conversion) of single alumina or modified alumina supported Rh catalysts.
  • the figures show perturbated aged TWC light off performance for (a) NO, (b) CO, and (c) THC conversions of washcoated (B5) reference Rh catalyst (aged) on single alumina support, and Rh catalysts (aged) on (B6) BaMnO 3 -, (B7) La 0.9 MnO 3 -, (B8) La 0.9 Mn 0.7 Zr 0.3 O 3 -, and (B9) La 0.9 Mn 0.9 Zr 0.1 O 3 -type perovskite-modified alumina support.
  • the modified supports were synthesized via incipient wetness impregnation method. Compared to the reference catalyst, pronounced improvements in TWC conversions were shown with perovskites-modified supports.
  • the figures show perturbated aged TWC light off performance for (a) NO, (b) CO, and (c) THC conversions of washcoated (B10) Reference Pd fully formulated catalyst (aged), and Pd catalysts (aged) with (B11) 10% BaMnO 3 -, (B12) 20% BaMnO 3 -, (B13) 20% La 0.9 MnO 3 -, (B14) 10% La 0.9 Mn 0.7 Zr 0.3 O 3 -, (B15) 10% La 0.9 Mn 0.9 Zr 0.1 O 3 -, and (B16) 10% LaFeO 3 -modified alumina-type perovskite-modified alumina support, and (B17) Reference Pd catalyst with 130 g/ft 3 Pd loading.
  • the order of overall TWC activity follows the order of Pd catalyst with 20%BaMnO 3 - alumina > 20% La 0.9 MnO 3 -alumina > 10% LaFeO 3 -alumina > 10% BaMnO 3 -alumina > 10% La 0.9 Mn 0.9 Zr 0.1 O 3 -alumina > 10% La 0.9 Mn 0.7 Zr 0.3 O 3 -alumina > Reference Pd (at 100 g/ft 3 ).
  • FIG.9a, FIG.9b and FIG.9c show TWC light off performance of fully formulated Pt catalysts with perovskite-modified supports.
  • the figures show perturbated aged TWC light off performance for (a) NO, (b) CO, and (c) THC conversions of washcoated (B22) Reference Pt (aged) fully formulated catalyst, and Pt catalysts (aged) with (B23) 10% BaMnO 3 -, (B24) 20% BaMnO 3 -, (B25) 10% La 0.9 MnO 3 -, (B26) 20% La 0.9 MnO 3 -, (B27) 10% CaMnO 3 -, (B28) 20% CaMnO 3 -, and (B29) 10% LaFeO 3- modified alumina support.
  • FIG. 10 shows cumulative NO x emission of fully formulated Pd-Rh catalysts with perovskite-modified supports.
  • FIG. 10 shows cumulative NO x emission during vehicle test of aged (B30) Reference PdRh fully formulated catalysts vs. PdRh catalysts (aged) with (B31) 10% BaMnO 3 (IWI)-, (B32) 10% BaMnO 3 (SD)-, and (B33) 20% BaMnO 3 (IWI)- modified alumina.
  • B31 10% BaMnO 3 (IWI)-
  • B32 10% BaMnO 3
  • SD BaMnO 3
  • B33 20% BaMnO 3

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