Precious metal-supported rare earth manganese-zirconium composite catalytic material and preparation method, and catalyst

Abstract

Provided are a precious metal-supported rare earth manganese-zirconium composite catalytic material and a preparation method. The catalytic material comprises a precious metal P and a rare earth manganese-zirconium composite oxide, the chemical general formula is P / REaMn bZrcLdO(2-δ)Dβ, the catalytic material has dual active sites, and the dual active sites are a P species active site and a rare earth manganese composite species active site; RE is a rare earth element, L is a cationic doping element, D is an anionic doping element, P is a platinum group metal element, 0.1≤a≤0.5, 0.05≤b≤0.3, 0.2≤c≤0.8, 0≤d≤0.2, 0≤δ≤0.1, 0≤β≤0.1, and a+b+c+d=1. The interaction between a metal and a composite carrier is regulated by means of pretreatment, so as to obtain a composite catalytic material having dual active sites to achieve an efficient synergistic effect.

Description

Precious metal supported rare earth manganese zirconium composite catalytic material and preparation method and catalyst

[0001] Cross-reference to related applications

[0002] The present application is based on and claims priority to Chinese patent applications with application number 202410785819.7, filed on June 18, 2024, and application number 202410787252.7, filed on June 18, 2024, the contents of which are hereby incorporated by reference in their entirety into the present application. TECHNICAL FIELD

[0003] The present application relates to the technical field of precious metal catalysts, in particular to a precious metal supported rare earth manganese zirconium composite catalytic material and a preparation method and catalyst thereof. BACKGROUND

[0004] Based on the concern for human health and the environment, how to eliminate automobile exhaust emissions has attracted widespread attention. In particular, for harmful exhaust gases such as CO, HC, NO, etc., the exhaust aftertreatment system is the most effective way of treatment, and the high-efficiency oxidation catalyst (DOC) plays an important role in removing CO, HC and improving the proportion of NO2.

[0005] At present, the supported precious metal catalyst is generally prepared by loading Pt on an Al-based carrier and calcining; Pt particles with high surface energy have a strong sintering tendency when working at high temperatures, and form larger particles through grain boundary migration. This phenomenon leads to a decrease in exposed precious metal active sites and a significant reduction in catalytic activity, greatly reducing the utilization rate of precious metals and increasing the cost of the catalyst. However, in order to improve the DOC catalytic efficiency, a certain amount of precious metal needs to be maintained. Manganese-based oxides have excellent oxidation activity and can greatly reduce the amount of precious metal used in DOC and improve the catalytic oxidation performance of NO. In addition, as the emission regulations become more stringent, the pollutant emission limit at low temperature is becoming lower and lower, so it is urgent to develop a low-temperature high-catalytic-activity DOC catalyst with extremely low precious metal content. SUMMARY

[0006] The purpose of the embodiments of the present application is to provide a precious metal supported rare earth manganese zirconium composite catalytic material and a preparation method, which combines the rare earth manganese zirconium composite oxide, which is both a carrier and an active component, with a small amount of high-activity precious metal by adjusting different pretreatment methods, to obtain a composite catalytic material with high-efficiency synergistic effect of double active sites. The double-structured composite catalytic material regulates the interaction between the precious metal and the composite carrier, and the Pt δ+ -O-Mn γ+ 、Pt δ+ -O-REγ+ The bonding strength is increased to enhance the adsorption capacity for target molecules, thereby improving the low-temperature catalytic oxidation capacity of NO in DOC materials, broadening the NO oxidation window, and improving high-temperature stability and durability. At the same time, the utilization rate of precious metals is increased, and the cost of catalytic materials is reduced.

[0007] To address the aforementioned technical problems, a first aspect of this invention provides a noble metal-supported rare earth manganese-zirconium composite catalytic material, wherein the catalytic material comprises noble metal P and rare earth manganese-zirconium composite oxide RE. a Mn b Zr c L d O (2-δ) D β Its general chemical formula is P / RE a Mn b Zr c L d O (2-δ) D β The catalytic material has dual active sites, which include: a P species active site and a rare earth manganese complex species active site;

[0008] Where RE represents rare earth elements, L represents cation dopant elements, D represents anion dopant elements, P represents platinum group metal elements, 0.1≤a≤0.5, 0.05≤b≤0.3, 0.2≤c≤0.8, 0≤d≤0.2, 0≤δ≤0.1, 0≤β≤0.1, and a+b+c+d=1.

[0009] Furthermore, the P species includes at least one of the metallic state and / or oxidation states of different valence positions of a noble metal.

[0010] Furthermore, the rare earth manganese complex species includes at least one of the following: mullite-type REMn2O5, perovskite-type REMnO3, Mn3O4, MnO, Mn2O3, MnO2, and amorphous rare earth manganese oxide species.

[0011] Furthermore, the rare earth manganese complex species include: mullite-type REMn2O5 and Mn3O4;

[0012] Based on the manganese oxide phase, the molar percentage of the mullite-type REMn2O5 phase oxide is 60.0% to 97.0%, the molar percentage of the Mn3O4 phase oxide is 3.0% to 38.0%, and the molar percentage of other manganese oxide phases is 0% to 2.0%.

[0013] Further, the molar percentage content of the mullite-type REMn2O5 phase oxide is 66.0% to 94.0%, the molar percentage content of the Mn3O4 phase oxide is 5.0% to 33.0%, and the molar percentage content of other manganese oxide phases is 0.01% to 1.0%.

[0014] Further, the other manganese oxide phases include one or a combination of one or more of a perovskite phase REMnO3, a MnO phase, a Mn2O3 phase, and a MnO2 phase.

[0015] Further, the primary particle size of the noble metal P is 0.1 nm to 5 nm, preferably 1 nm to 3 nm.

[0016] The primary particle size of the rare earth manganese zirconium composite oxide is 3 nm to 40 nm, preferably 6 nm to 20 nm.

[0017] Further, the loading of the noble metal P is 0.01% to 0.3% by mass, preferably 0.05% to 0.2%.

[0018] The proportion of the metallic state in the noble metal P accounts for 15% to 85% of the total amount of the noble metal P, preferably 35% to 65%.

[0019] Further, the noble metal P includes at least one of platinum group metals Pt, Pd, Rh, Ir, Os, and Ru, preferably at least one of Pt, Pd, and Rh.

[0020] Further, the rare earth element RE includes at least one of La, Ce, Pr, Nd, Sm, Eu, Gd, Yb, and Y.

[0021] The doping element L includes at least one of transition metal elements, alkaline earth metal elements, and Al, Si, and Sn, preferably at least one of Fe, Co, Ni, Cu, Zn, V, Ti, Cr, Mo, W, Sn, Nb, Al, Si, Ga, Ge, In, Hf, Ba, Sr, Mg, and Ca.

[0022] The doping element D includes at least one of anions N, P, F, and S.

[0023] Correspondingly, a second aspect of the embodiment of the present application provides a preparation method of a noble metal supported rare earth manganese zirconium composite catalytic material, for preparing the noble metal supported rare earth manganese zirconium composite catalytic material, including the following steps:

[0024] The compound of the noble metal P is ultrasonically dispersed into a preset solvent to obtain a compound solution of the noble metal P, wherein the preset solvent includes at least one of deionized water, ethanol, and acetone.

[0025] adding the compound solution of the noble metal P into the slurry containing rare earth manganese zirconium composite catalyst RE a Mn b Zr c L d O (2-δ) D β , and then drying and calcining to obtain P / RE a Mn b Zr c L d O (2-δ) D β precursor;

[0026] performing heat treatment on the P / RE a Mn b Zr c L d O (2-δ) D β precursor under preset atmosphere conditions to obtain P / RE a Mn b Zr c L d O (2-δ) D β finished product with double active sites.

[0027] Optionally, before the step of ultrasonically dispersing the compound of the noble metal P into the preset solvent, the method further comprises:

[0028] mixing salt solutions of all zirconium, all RE and all cation-doped elements L, adding an alkaline substance to perform a precipitation reaction, and then performing filtration, washing, drying and calcining to obtain rare earth zirconium oxide containing RE and L;

[0029] mixing the salt solution of all manganese with the rare earth zirconium oxide in one or more steps to obtain a composite compound precursor, wherein the multiple steps refer to adding manganese in steps;

[0030] performing heat treatment on the composite compound precursor to obtain a rare earth manganese zirconium composite catalyst RE a Mn b Zr c L d O (2-δ) D β .

[0031] Optionally, before the step of ultrasonically dispersing the compound of the noble metal P into the preset solvent, the method further comprises:

[0032] Mixing the salt solution of all zirconium, part of RE and / or part of cation-doped element L, adding alkaline substance to carry out precipitation reaction, after filtration, washing, drying and calcination, the rare earth zirconium oxide containing RE and L is obtained;

[0033] Mixing the salt solution of all manganese, the rest of RE and / or the rest of cation-doped element L with the rare earth zirconium oxide in one or more steps, wherein the multiple steps refer to adding manganese step by step, to obtain a composite compound precursor;

[0034] After heat treatment of the composite compound precursor, the rare earth manganese zircon composite catalyst RE a Mn b Zr c L d O (2-δ) D β .

[0035] Further, the drying process temperature after the precipitation reaction is 60-200°C, preferably 80-180°C, and the drying process time is 1-24h, preferably 2-12h;

[0036] The calcination process temperature after the precipitation reaction is 500-1000°C, preferably 600-900°C, and the calcination process time is 1-20h, preferably 2-10h;

[0037] The heat treatment process temperature of the composite compound precursor is 100-1000°C, preferably 200-900°C, and the heat treatment time is 1-20h, preferably 3-10h.

[0038] Further, the compound of the noble metal P includes at least one of chloride salt, nitrate salt, acetate salt, 2-hydroxyethylammonium hexahydroxyl P, diethanolamine hexahydroxyl P acid and citrate aqueous solution.

[0039] Further, the drying process temperature of the slurry is 60-200°C, and the drying process time is 1-24h;

[0040] The calcination process temperature of the slurry after drying treatment is 300-900°C, and the calcination process time is 2-12h;

[0041] The heat treatment process temperature of the precursor under the preset atmosphere condition is 200-900°C, preferably 350-750°C;

[0042] The heat treatment process time of the precursor under the preset atmosphere condition is 0.5-14h, preferably 3-10h.

[0043] Further, the preset atmosphere condition comprises at least one of air, O2, CO, Ar, H2, CO2, N2 and water vapor.

[0044] Correspondingly, a third aspect of the embodiment of the present application provides a catalyst comprising the above-mentioned precious metal supported rare earth manganese zirconium composite catalytic material, which is applied to the fields of motor vehicle exhaust purification, industrial organic waste gas treatment, natural gas catalytic combustion, petroleum chemical industry, hydrogen energy and batteries.

[0045] The above technical solution of the embodiment of the present application has the following beneficial technical effects:

[0046] By regulating different pretreatment methods, the rare earth manganese zirconium composite oxide which is both a carrier and an active component is combined with a small amount of high-activity precious metal to double-construct a composite catalytic material, the interaction between the metal and the composite carrier is regulated, the different bond strengths of Pt δ+ -O-Mn γ+ , Pt δ+ -O-RE γ+ bond between the active species of the surface precious metal and the active composite rare earth manganese zirconium are regulated to obtain a composite catalytic material with double active sites and high efficiency synergistic effect; and the oxygen vacancy content is increased, the electron transfer between the precious metal and the rare earth manganese oxide is promoted, the electronic structure of the precious metal is regulated, the target molecule adsorption capacity is improved, the reaction energy barrier of the rate-determining step is reduced, the NO low-temperature catalytic oxidation capacity of the DOC material is improved, the NO oxidation window is widened, the high-temperature stability and durability are improved, the precious metal utilization rate is improved, and the cost of the catalytic material is reduced. BRIEF DESCRIPTION OF DRAWINGS

[0047] Fig. 1 is a flow chart of a preparation method of the precious metal supported rare earth manganese zirconium composite catalytic material provided by the embodiment of the present application. DETAILED DESCRIPTION

[0048] In order to make the object, technical scheme and advantages of the present application more clear, the present application is further described in detail below with reference to the specific embodiments and the accompanying drawings. It should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present application. In addition, in the following description, the description of the known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present application.

[0049] A first aspect of the embodiment of the present application provides a precious metal supported rare earth manganese zirconium composite catalytic material, which comprises a precious metal P and a rare earth manganese zirconium composite oxide RE a Mn b Zr c L d O (2-δ) D β , and the chemical general formula is P / RE a Mn b Zrc L d O (2-δ) D β , the catalytic material has double active sites, the double active sites comprising: P species active sites and rare earth manganese complex species active sites; wherein RE is a rare earth element, L is a cation doping element, D is an anion doping element, P is a platinum group metal element, 0.1≤a≤0.5, 0.05≤b≤0.3, 0.2≤c≤0.8, 0≤d≤0.2, 0≤δ≤0.1, 0≤β≤0.1, and a+b+c+d=1.

[0050] The catalytic material is obtained by regulating different pretreatment methods, combining the rare earth manganese zircon composite oxide which is both a carrier and an active component with a small amount of high-activity noble metal, double-constructing the composite catalytic material, regulating the interaction between the noble metal and the composite carrier, changing the bonding strength between the active species of the surface noble metal and the active composite rare earth manganese zirconium, and obtaining the composite catalytic material with double active sites and high-efficiency synergistic effect, so as to improve the NO low-temperature catalytic oxidation capacity, broaden the NO oxidation window, improve the high-temperature stability and durability of the DOC material.

[0051] Further, the P species comprises at least one of a metallic state and / or different valence oxidation states of the noble metal. Specifically, the P species can only contain the metallic state of the noble metal, can include one or more of different valence oxidation states, or can contain one or more of the metallic state and different valence oxidation states. Optionally, the valence of the oxidation state of the noble metal comprises +2 valence and +4 valence.

[0052] Further, the rare earth manganese complex species comprises at least one of a mullite type REMn2O5, a perovskite type REMnO3, Mn3O4, MnO, Mn2O3, MnO2 and an amorphous rare earth manganese oxide species.

[0053] Further, the primary particle size of the noble metal P is 0.1nm-5nm, preferably 1nm-3nm; and the primary particle size of the rare earth manganese zirconium composite oxide is 3nm-40nm, preferably 6nm-20nm.

[0054] Further, the loading of the noble metal P is 0.01%-0.3% by mass, preferably 0.05%-0.2%; and the proportion of the metallic state in the total amount of the noble metal P is 15%-85%, preferably 35%-65%.

[0055] Further, the noble metal P comprises at least one of platinum group metals Pt, Pd, Rh, Ir, Os and Ru, and preferably at least one of Pt, Pd and Rh.

[0056] Further, the rare earth element RE includes at least one of La, Ce, Pr, Nd, Sm, Eu, Gd, Yb and Y;

[0057] The doping element L includes at least one of a transition metal element, an alkaline earth metal element and Al, Si and Sn, and preferably at least one of Fe, Co, Ni, Cu, Zn, V, Ti, Cr, Mo, W, Sn, Nb, Al, Si, Ga, Ge, In, Hf, Ba, Sr, Mg and Ca;

[0058] The doping element D includes at least one of anions N, P, F and S.

[0059] In another specific embodiment of the present application, the rare earth manganese composite species includes mullite-type REMn2O5 and Mn3O4. The molar percentage content of the mullite-type REMn2O5 phase oxide is 60.0% to 97.0%, the molar percentage content of the Mn3O4 phase oxide is 3.0% to 38.0%, and the molar percentage content of other manganese oxide phases is 0 to 2.0%, in terms of manganese oxide phases.

[0060] Further, the molar percentage content of the mullite-type REMn2O5 phase oxide is 66.0% to 94.0%, the molar percentage content of the Mn3O4 phase oxide is 5.0% to 33.0%, and the molar percentage content of other manganese oxide phases is 0.01% to 1.0%.

[0061] Specifically, the other manganese oxide phases include one or a combination of one or more of perovskite-type REMnO3, MnO phase, Mn2O3 phase and MnO2 phase.

[0062] By adjusting the ratio of RE to Mn and using pre-set atmosphere calcination and other means to construct a rare earth manganese compound catalytic material with a mullite phase REMn2O5, Mn3O4 and other manganese oxide composite phase structure, a two-phase composite interface of the composite phase structure is constructed, the oxygen vacancy content of the composite phase structure catalytic material is increased, the electron transfer and oxygen transport capacity at the interface is improved, the NO adsorption and intermediate storage capacity of the composite phase structure catalytic material is enhanced, the synergistic catalytic effect between the two phases is formed, and the low-temperature catalytic oxidation capacity of NO is improved. At the same time, the main phase of the composite phase structure catalytic material is the REMn2O5 phase, and the second phase manganese oxide (mainly Mn3O4 phase oxide) grows in situ on the main phase, is uniformly distributed, inhibits the sintering and agglomeration of the high-activity REMn2O5 phase at high temperature, and enhances the stability of the high-temperature environment.

[0063] Correspondingly, referring to Fig. 1, the second aspect of the embodiment of the present application provides a preparation method of a precious metal supported rare earth manganese zirconium composite catalytic material, which is used for preparing the precious metal supported rare earth manganese zirconium composite catalytic material and comprises the following steps:

[0064] S2, dispersing a compound of the precious metal P into a preset solvent by ultrasonic to obtain a compound solution of the precious metal P, wherein the preset solvent comprises at least one of deionized water, ethanol and acetone.

[0065] S3, adding the compound solution of the precious metal P into a slurry containing the rare earth manganese zirconium composite catalytic material RE a Mn b Zr c L d O (2-δ) D β , and preparing a P / RE a Mn b Zr c L d O (2-δ) D β precursor by drying and calcining.

[0066] S4, performing heat treatment on the P / RE a Mn b Zr c L d O (2-δ) D β precursor under a preset atmosphere to obtain a finished product P / RE a Mn b Zr c L d O (2-δ) D β with double active sites.

[0067] The preparation method above impregnates a small amount of a precious metal P salt solution into the surface of RE a Mn b Zr c L d O (2-δ) D β , uniformly mixes, dries and calcines to obtain P / RE a Mn b Zr c L d O (2-δ) D β . By regulating different pretreatment methods, the rare earth manganese zirconium composite oxide which is both a carrier and an active component is combined with a small amount of a high-activity precious metal, the interaction between the precious metal and the composite carrier and the different bonding strength of Pt δ+ -O-Mn γ+ , Ptδ+ -O-RE γ+ bond, promoting electron transfer between noble metal and rare earth manganese oxide, double-structured composite catalytic material, obtaining composite catalytic material with double active sites and high efficiency synergistic effect, to improve the NO low-temperature catalytic oxidation ability of DOC material, broaden the NO oxidation window, high temperature stability and durability.

[0068] Optionally, the step S2 further includes a process of preparing a rare earth manganese zirconium composite catalyst RE a Mn b Zr c L d O (2-δ) D β , which can adopt the following two ways:

[0069] The preparation process of optional way one is as follows:

[0070] S11, mix all zirconium, all RE and all cation-doped element L salt solution, add alkaline substance for precipitation reaction, after filtration, washing, drying and calcination, obtain rare earth zirconium oxide containing RE and L.

[0071] S12, mix all manganese salt solution with rare earth zirconium oxide in one step or multiple steps to obtain a composite compound precursor, wherein the multiple steps refer to adding manganese in steps.

[0072] S13, after heat treatment of the composite compound precursor, obtain a rare earth manganese zirconium composite catalyst RE a Mn b Zr c L d O (2-δ) D β .

[0073] In the preparation process of the above rare earth manganese zirconium composite catalyst, all zirconium, all RE and all cation-doped element L are added and mixed in step S11.

[0074] The preparation process of optional way two is as follows:

[0075] S11, mix all zirconium, part of RE and / or part of cation-doped element L salt solution, add alkaline substance for precipitation reaction, after filtration, washing, drying and calcination, obtain rare earth zirconium oxide containing RE and L.

[0076] S12, mix all manganese, remaining RE and / or remaining cation-doped element L salt solution with rare earth zirconium oxide in one step or multiple steps to obtain a composite compound precursor, wherein the multiple steps refer to adding manganese in steps.

[0077] S13, after heat treatment of the composite compound precursor, a rare earth manganese zircon composite catalyst RE is obtained a Mn b Zr c L d O (2-δ) D β .

[0078] In the preparation process of the rare earth manganese zircon composite catalyst, all the zirconium, part of the RE and part of the cation doping element L are added and mixed in step S11.

[0079] Alternatively, there are two ways, the first is to add all the zirconium, all the RE and part of the cation doping element L in step S11, and mix all the manganese and the remaining cation doping element L in step S12; the second is to add all the zirconium, part of the RE and all the cation doping element L in step S11, and mix all the manganese and the remaining RE in step S12.

[0080] Further, the drying process temperature in step S11 is 60-200°C, preferably 80-180°C, and the drying process time is 1-24h, preferably 2-12h;

[0081] The calcination process temperature in step S11 is 500-1000°C, preferably 600-900°C, and the calcination process time is 1-20h, preferably 2-10h;

[0082] The heat treatment process temperature in step S13 is 100-1000°C, preferably 200-900°C, and the heat treatment time is 1-20h, preferably 3-10h.

[0083] Further, the compound of the noble metal P includes at least one of a chloride salt, a nitrate salt, an acetate salt, 2-hydroxyethylammonium hexahydroxyl P, diethanolamine hexahydroxyl P acid and a citrate aqueous solution.

[0084] Further, the drying process temperature in step S3 is 60-200°C, and the drying process time is 1-24h; the calcination process temperature in step S3 is 300-900°C, and the calcination process time is 2-12h; the heat treatment process temperature in step S4 is 200-900°C, preferably 350-750°C; the heat treatment process time in step S4 is 0.5-14h, preferably 3-10h. By controlling the drying, calcination and heat treatment temperature and time, the interaction between the noble metal and the composite carrier is beneficial to the regulation, the synergistic effect of the double active sites is promoted, and the catalytic activity is improved.

[0085] Further, the preset atmosphere condition in step S4 includes at least one of air, O2, CO, Ar, H2, CO2, N2 and water vapor H2O(g). By controlling the preset atmosphere, the carrier oxygen vacancy concentration is improved, the electron transfer between the noble metal and the rare earth manganese oxide is promoted, the synergistic effect of the double active sites is facilitated, and the catalytic activity is improved.

[0086] Advantages of the present application:

[0087] The present application provides a noble metal supported rare earth manganese zirconium composite catalytic material and a preparation method and a catalyst. The noble metal supported rare earth manganese zirconium composite catalytic material has double active sites, including noble metal P and rare earth manganese zirconium composite oxide RE a Mn b Zr c L d O (2-δ) D β , the structure is P / RE a Mn b Zr c L d O (2-δ) D β with the primary particle size of the noble metal being 0.1-5nm and the primary particle size of the rare earth manganese zirconium composite oxide being 6-20nm. By adjusting different pretreatment methods, the rare earth manganese zirconium composite oxide which is both a carrier and an active component is combined with a small amount of high-activity noble metal, the interaction strength between the noble metal and the composite carrier is adjusted, and a composite catalytic material with double active site synergistic effect is obtained by double construction. The noble metal supported rare earth manganese zirconium composite catalytic material can be used for efficient removal of pollutants such as NO, is beneficial to improve the NO low-temperature oxidation performance, widen the NO oxidation window and improve the high-temperature stability and durability.

[0088] In the following, the above preparation method is described in detail by a number of comparative examples and a number of examples:

[0089] Comparative Example 1

[0090] A certain volume of liquid platinum nitrate salt solution was taken according to the Pt loading of 0.18wt%, mixed uniformly with alumina slurry, dried at 100℃ for 12h, and then heat treated at 450℃ for 5h to obtain 0.18wt% Pt γ / Al2O3. The above sample was tested for catalytic performance, the maximum conversion rate of NO was 32.72%, the temperature corresponding to the maximum conversion rate of NO was 398.9℃, and the main active site was a single active site of noble metal species.

[0091] Comparative Example 2

[0092] A certain volume of liquid state platinum nitrate solution was mixed with alumina slurry at a Pt loading of 0.18wt%, and then dried at 200°C for 1h, and then calcined at 550°C for 3h to obtain 0.18wt% Pt / Al2O3. γ The sample was tested for catalytic performance, and the maximum NO conversion rate was 64.49%, and the temperature corresponding to the maximum NO conversion rate was 337.4°C. The main active site was a single active site of a noble metal species.

[0093] Comparative Example 3

[0094] A certain volume of liquid state palladium nitrate solution was mixed with alumina slurry at a Pd loading of 0.18wt%, and then dried at 120°C for 8h, and then calcined at 400°C for 6h to obtain 0.18wt% Pd / Al2O3. γ The sample was tested for catalytic performance, and the maximum NO conversion rate was 24.28%, and the temperature corresponding to the maximum NO conversion rate was 389.7°C. The main active site was a single active site of a noble metal species.

[0095] Comparative Example 4

[0096] A certain volume of liquid state rhodium nitrate solution was mixed with alumina slurry at a Rh loading of 0.18wt%, and then dried at 180°C for 8h, and then calcined at 500°C for 4h to obtain 0.18wt% Rh / Al2O3. γ The sample was tested for catalytic performance, and the maximum NO conversion rate was 27.32%, and the temperature corresponding to the maximum NO conversion rate was 403.6°C. The main active site was a single active site of a noble metal species.

[0097] Comparative Example 5

[0098] Ce 0.10 Y 0.05 Mn 0.05 Zr 0.80 The sample was tested for catalytic performance, and the maximum NO conversion rate was 64.41%, and the temperature corresponding to the maximum NO conversion rate was 342.1°C. The main active site was a single active site of a rare earth manganese composite species.

[0099] Comparative Examples 1-4 were aluminum-based noble metal catalysts, and Comparative Example 5 was a rare earth manganese zirconium composite oxide without P loading. The specific parameters are shown in Table 1.

[0100] Table 1

[0101] Example 1

[0102] A certain volume of liquid salt solution of platinum nitrate was taken in an amount of 0.18wt% Rh loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.20 Nd 0.05 Mn 0.20 Zr 0.50 Si 0.05 O2 slurry, and dried at a temperature of 100°C for 5h, and then high-temperature heat treated at 900°C for 2h, and calcined at 800°C for 14h in a N2 atmosphere, to obtain 0.18wt% Rh / Ce 0.20 Nd 0.05 Mn 0.20 Zr 0.50 Si 0.05 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 68%, and the molar percentage content of the Mn3O4 phase oxide was 32%, calculated on the basis of the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 59.91%, and the temperature corresponding to the maximum conversion rate of NO was 360.5°C. The main active sites were the double active centers of the noble metal Rh species and the rare earth manganese composite species.

[0103] Examples 2-44: The preparation method was the same as Example 1, and the main active sites were the double active centers of the noble metal species and the rare earth manganese composite species.

[0104] Example 2

[0105] A certain volume of liquid salt solution of chloroplatinic acid was taken in an amount of 0.18wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.20 Pr 0.15 Mn 0.15 Zr 0.50 O2 slurry, and dried at a temperature of 180°C for 1h, and then high-temperature heat treated at 500°C for 4h, and calcined at 550°C for 2h in a H2 atmosphere, to obtain 0.18wt% Pt / Ce 0.20 Pr 0.15 Mn 0.15 Zr 0.50 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 86.7%, the molar percentage content of the Mn3O4 phase oxide was 12.5%, and the molar percentage content of other manganese oxide phases was 0.8%, calculated on the basis of the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 81.49%, and the temperature corresponding to the maximum conversion rate of NO was 231.7°C.

[0106] Example 3

[0107] A certain volume of liquid salt solution of platinum nitrate was taken in an amount of 0.18wt% Pt loading, and mixed with the rare earth manganese zirconium composite oxide Ce 0.15 Nd 0.05 Pr 0.05 Eu 0.05 Mn 0.20 Zr 0.50 O 1.98 S 0.02 The slurry was mixed uniformly, dried at a temperature of 100°C for 6h, then high-temperature heat treated at 500°C for 4h, and calcined at 850°C for 6h in a water vapor atmosphere to obtain 0.18wt% Pt / Ce 0.15 Nd 0.05 Pr 0.05 Eu 0.05 Mn 0.20 Zr 0.50 O 1.98 S 0.02 . Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 81.2%, and the molar percentage content of the Mn3O4 phase oxide was 18.8% based on the manganese oxide phase. The above sample was tested for catalytic performance, and the maximum conversion rate of NO was 81.21%, and the temperature corresponding to the maximum conversion rate of NO was 235.8°C.

[0108] Example 4

[0109] A certain volume of liquid salt solution of platinum nitrate and palladium nitrate was taken in an amount of 0.03wt% Pd and 0.15wt% Pt loading, and mixed with the rare earth manganese zirconium composite oxide Ce 0.14 Eu 0.03 Mn 0.16 Zr 0.58 Al 0.04 Si 0.05 O2The slurry was mixed uniformly, dried at a temperature of 60°C for 15h, then high-temperature heat treated at 600°C for 2h, and calcined at 450°C for 3h in a H2 atmosphere to obtain 0.18wt% PtPd / Ce 0.14 Eu 0.03 Mn 0.16 Zr 0.58 Al 0.04 Si 0.05 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 74.5%, the molar percentage content of the Mn3O4 phase oxide was 24.5%, and the molar percentage content of other manganese oxide phases was 1% based on the manganese oxide phase. The above sample was tested for catalytic performance, and the maximum conversion rate of NO was 84.37%, and the temperature corresponding to the maximum conversion rate of NO was 234.9°C.

[0110] Example 5

[0111] A certain volume of liquid salt solution of platinum nitrate and rhodium nitrate was taken in the loading amount of 0.05wt% Pt and 0.15wt% Rh, and was mixed with rare earth manganese zirconium composite oxide Ce 0.20 La 0.05 Y 0.05 Mn 0.25 Zr 0.40 Fe 0.05 O2was mixed uniformly, and was dried at a temperature of 80°C for 10h, and then was high-temperature heat treated at 500°C for 4h, and was calcined at 750°C under CO atmosphere for 4h, to obtain 0.18wt% PtRh / Ce 0.20 La 0.05 Y 0.05 Mn 0.25 Zr 0.40 Fe 0.05 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide was 75%, the molar percentage content of the Mn3O4 phase oxide was 24.7%, and the molar percentage content of other manganese oxide phases was 0.3%, calculated based on the manganese oxide phase. The above sample was tested for catalytic performance, and the maximum conversion rate of NO was 73.22%, and the temperature corresponding to the maximum conversion rate of NO was 295.7°C.

[0112] Example 6

[0113] A certain volume of liquid salt solution of platinum nitrate and rhodium nitrate was taken in the loading amount of 0.03wt% Pd, 0.03wt% Pt and 0.12wt% Rh, and was mixed with rare earth manganese zirconium composite oxide Ce 0.20 La 0.05 Y 0.05 Mn 0.20 Zr 0.50 O 1.98 N 0.02 was mixed uniformly, and was dried at a temperature of 160°C for 5h, and then was high-temperature heat treated at 600°C for 4h, and was calcined at 300°C under water vapor atmosphere for 12h, to obtain 0.18wt% PtPdRh / Ce 0.20 La 0.05 Y 0.05 Mn 0.20 Zr 0.50 O 1.98 N 0.02 . Among them, the molar percentage content of the mullite type REMn2O5 phase oxide was 87.5%, the molar percentage content of the Mn3O4 phase oxide was 11.5%, and the molar percentage content of other manganese oxide phases was 1%, calculated based on the manganese oxide phase. The above sample was tested for catalytic performance, and the maximum conversion rate of NO was 67.29%, and the temperature corresponding to the maximum conversion rate of NO was 347.3°C.

[0114] Example 7

[0115] A volume of liquid salt solution of platinum nitrate was taken in an amount of 0.20wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.30 Mn 0.10 Zr 0.50 Fe 0.05 Co 0.05 O2was mixed uniformly, dried at a temperature of 90°C for 16h, then high-temperature heat treated at 700°C for 4h, and calcined at 700°C under a water vapor atmosphere for 8h to obtain 0.05wt% Pt / Ce 0.30 Mn 0.10 Zr 0.50 Fe 0.05 Co 0.05 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 77.5%, and the molar percentage content of the Mn3O4 phase oxide was 22.5% based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 83.91%, and the temperature corresponding to the maximum conversion rate of NO was 234.5°C.

[0116] Example 8

[0117] A volume of liquid salt solution of platinum nitrate was taken in an amount of 0.20wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.40 Nd 0.05 Mn 0.20 Zr 0.20 Fe 0.10 Sn 0.05 O2was mixed uniformly, dried at a temperature of 110°C for 4h, then high-temperature heat treated at 400°C for 5h, and calcined at 400°C under a water vapor atmosphere for 14h to obtain 0.18wt% Pt / Ce 0.40 Nd 0.05 Mn 0.20 Zr 0.20 Fe 0.10 Sn 0.05 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 92.3%, and the molar percentage content of the Mn3O4 phase oxide was 7.7% based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 71.82%, and the temperature corresponding to the maximum conversion rate of NO was 254.5°C.

[0118] Example 9

[0119] A volume of liquid salt solution of platinum nitrate was taken in an amount of 0.20wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.40 Nd 0.05 Mn 0.20 Zr 0.30 Hf0.05 The O2 slurry was mixed uniformly, dried at 200°C for 1 h, then high-temperature heat treated at 700°C for 4 h, and calcined at 800°C for 14 h in a CO2 atmosphere to obtain 0.18wt% Pt / Ce 0.40 Nd 0.05 Mn 0.20 Zr 0.30 Hf 0.05 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 70%, and the molar percentage content of the Mn3O4 phase oxide was 30% based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 62.35%, and the temperature corresponding to the maximum conversion rate of NO was 351.3°C.

[0120] Example 10

[0121] A certain volume of liquid salt solution of platinum nitrate was taken in an amount of 0.18wt% Pt loading, and mixed with rare earth manganese zirconium composite oxide Ce 0.15 La 0.04 Nd 0.04 Y 0.06 Mn 0.16 Zr 0.55 O 1.98 N 0.01 The slurry was mixed uniformly, dried at 150°C for 5 h, then high-temperature heat treated at 400°C for 5 h, and calcined at 650°C for 10 h in a water vapor atmosphere to obtain 0.18wt% Pt / Ce 0.15 La 0.04 Nd 0.04 Y 0.06 Mn 0.16 Zr 0.55 O 1.98 N 0.01 . Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 75%, and the molar percentage content of the Mn3O4 phase oxide was 25% based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 82.67%, and the temperature corresponding to the maximum conversion rate of NO was 237.4°C.

[0122] Example 11

[0123] A certain volume of liquid salt solution of platinum nitrate and palladium nitrate was taken in an amount of 0.06wt% Pd and 0.12wt% Pt loading, and mixed with rare earth manganese zirconium composite oxide Ce 0.14 La 0.03 Gd 0.04 Ho 0.05 Mn 0.15 Zr 0.58 Cr 0.50The O2 slurry was mixed uniformly, dried at 150°C for 5h, then high-temperature heat treated at 550°C for 1h, and calcined at 500°C for 3h in H2 atmosphere to obtain 0.18wt% PtPd / Ce 0.14 La 0.03 Gd 0.04 Ho 0. 05 Mn 0.15 Zr 0.58 Cr 0.50 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 74%, and the molar percentage content of the Mn3O4 phase oxide was 26% based on the manganese oxide phase. The above sample was subjected to catalytic performance test, and the maximum conversion rate of NO was 82.14%, and the temperature corresponding to the maximum conversion rate of NO was 248.4°C.

[0124] Example 12

[0125] A certain volume of liquid salt solution of platinum nitrate and rhodium nitrate was taken according to the loading amount of 0.06wt% Pt and 0.12wt% Rh, and mixed with rare earth manganese zirconium composite oxide Ce 0.20 La 0.02 Nd 0.05 Y 0.03 Mn 0.25 Zr 0.45 The O2 slurry was mixed uniformly, dried at 100°C for 5h, then high-temperature heat treated at 600°C for 5h, and calcined at 700°C for 2h in CO atmosphere to obtain 0.18wt% PtRh / Ce 0.20 La 0.02 Nd 0.05 Y 0.03 Mn 0.25 Zr 0.45 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 74%, and the molar percentage content of the Mn3O4 phase oxide was 26% based on the manganese oxide phase. The above sample was subjected to catalytic performance test, and the maximum conversion rate of NO was 82.14%, and the temperature corresponding to the maximum conversion rate of NO was 248.4°C.

[0126] Example 13

[0127] A certain volume of liquid salt solution of palladium nitrate, platinum nitrate and rhodium nitrate was taken according to the loading amount of 0.03wt% Pd, 0.06wt% Pt and 0.09wt% Rh, and mixed with rare earth manganese zirconium composite oxide Ce 0.20 La 0.05 Y 0. 05 Mn 0.20 Zr 0.50The O2 slurry was mixed uniformly, dried at 90°C for 10h, then high-temperature heat treated at 500°C for 5h, and calcined at 350°C for 12h in a water vapor atmosphere to obtain 0.18wt% PtPdRh / Ce 0. 20 La 0.05 Y 0.05 Mn 0.20 Zr 0.50 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 79%, and the molar percentage content of the Mn3O4 phase oxide was 21% based on the manganese oxide phase. The above sample was subjected to catalytic performance test, and the maximum conversion rate of NO was 70.11%, and the temperature corresponding to the maximum conversion rate of NO was 339.1°C.

[0128] Example 14

[0129] A certain volume of liquid platinum nitrate salt solution was taken according to a Pt loading of 0.25wt%, and mixed with a rare earth manganese-zirconium composite oxide Ce 0.20 La 0.05 Pr 0.05 Mn 0.10 Zr 0.50 Fe 0.10 O2 slurry was mixed uniformly, dried at 100°C for 14h, then high-temperature heat treated at 600°C for 3h, and calcined at 750°C for 3h in a water vapor atmosphere to obtain 0.25wt% Pt / Ce 0.20 La 0.05 Pr 0.05 Fe 0.10 M n0.10 Zr 0.50 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 84%, and the molar percentage content of the Mn3O4 phase oxide was 16% based on the manganese oxide phase. The above sample was subjected to catalytic performance test, and the maximum conversion rate of NO was 85.51%, and the temperature corresponding to the maximum conversion rate of NO was 231.3°C.

[0130] Example 15

[0131] A certain volume of liquid platinum nitrate salt solution was taken according to a Pt loading of 0.18wt%, and mixed with a rare earth manganese-zirconium composite oxide Ce 0.20 Sm 0.20 La 0.02 Nd 0.05 Y 0.03 Mn 0.10 Zr 0.30 Co 0.10 O2 slurry was mixed uniformly, dried at 100°C for 5h, then high-temperature heat treated at 600°C for 4h, and calcined at 600°C for 10h in a water vapor atmosphere to obtain 0.18wt% Pt / Ce0.20 Sm 0.20 La 0.02 Nd 0.05 Y 0.03 Mn 0.10 Zr 0.30 Co 0. 10 O2. Among them, the molar percentage content of the mullite type REMn205 phase oxide is 87.5%, and the molar percentage content of the Mn304 phase oxide is 12.5% based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 79.87%, and the temperature corresponding to the maximum conversion rate of NO is 241.2°C.

[0132] Example 16

[0133] A certain volume of liquid salt solution of platinum nitrate is taken in an amount of 0.18wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.40 La 0.02 Nd 0.05 Y 0.03 Mn 0.20 Zr 0.30 O2slurry, and dried at a temperature of 180°C for 3h, and then high-temperature heat treated at 650°C for 4h, and calcined at 700°C for 8h in a CO2 atmosphere, to obtain 0.18wt% Pt / Ce 0.40 La 0.02 Nd 0.05 Y 0.03 Mn 0.20 Zr 0.30 O2. Among them, the molar percentage content of the mullite type REMn205 phase oxide is 87.5%, and the molar percentage content of the Mn304 phase oxide is 12.5% based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 79.87%, and the temperature corresponding to the maximum conversion rate of NO is 241.2°C.

[0134] Example 17

[0135] A certain volume of liquid salt solution of platinum nitrate is taken in an amount of 0.18wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.20 La 0.05 Nd 0.05 Mn 0.20 Zr 0.50 O 1.98 F 0.04 slurry, and dried at a temperature of 120°C for 3h, and then high-temperature heat treated at 500°C for 2h, and calcined at 600°C for 2h in a CO atmosphere, to obtain 0.18wt% Pt / Ce 0.20 La 0.05 Nd 0.05 Mn0.20 Zr 0.50 O 1.98 F 0.04 The molar percentage content of the mullite-type REMn2O5 phase oxide is 82%, and the molar percentage content of the Mn3O4 phase oxide is 18%. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 80.19%, and the temperature corresponding to the maximum conversion rate of NO is 234.3°C.

[0136] Example 18

[0137] A certain volume of liquid salt solution of platinum nitrate and palladium nitrate is taken according to the loading amount of 0.09wt%Pd and 0.09wt%Pt, and mixed with the rare earth manganese zirconium composite oxide Ce 0.40 Sc 0.02 Yb 0.05 Y 0.03 Mn 0.10 Zr 0.30 Ti 0. 10 O2The slurry is mixed uniformly, dried at a temperature of 140°C for 3h, then high-temperature heat treated at 500°C for 3h, and calcined at 400°C for 4h in a H2atmosphere, to obtain 0.18wt%PtPd / Ce 0.40 Sc 0.02 Yb 0.05 Y 0. 03 Mn 0.10 Zr 0.30 Ti 0.10 O2The molar percentage content of the mullite-type REMn2O5 phase oxide is 77%, and the molar percentage content of the Mn3O4 phase oxide is 23%. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 81.32%, and the temperature corresponding to the maximum conversion rate of NO is 256.1°C.

[0138] Example 19

[0139] A certain volume of liquid salt solution of platinum nitrate and rhodium nitrate is taken according to the loading amount of 0.09wt%Pt and 0.09wt%Rh, and mixed with the rare earth manganese zirconium composite oxide Ce 0.20 La 0.02 Nd 0.03 Sm 0.03 Y 0.02 Mn 0.20 Zr 0.50 O2The slurry is mixed uniformly, dried at a temperature of 120°C for 3h, then high-temperature heat treated at 450°C for 5h, and calcined at 650°C for 3h in a CO atmosphere, to obtain 0.18wt%PtRh / Ce 0.20 La 0.02 Nd0.03 Sm 0.03 Y 0.02 Mn 0.20 Zr 0.50 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 86%, and the molar percentage content of the Mn3O4 phase oxide is 14% based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 77.08%, and the temperature corresponding to the maximum conversion rate of NO is 260.2°C.

[0140] Example 20

[0141] A certain volume of liquid salt solution of palladium nitrate, platinum nitrate and rhodium nitrate is taken according to the loading amount of 0.06wt%Pd, 0.06wt%Pt and 0.06wt%Rh, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.14 La 0.05 Nd 0.04 Y 0.05 Mn 0.16 Zr 0.60 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 86%, and the molar percentage content of the Mn3O4 phase oxide is 14% based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 77.08%, and the temperature corresponding to the maximum conversion rate of NO is 260.2°C. 0.14 La 0.05 Nd 0.04 Y 0.05 Mn 0.16 Zr 0.60 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 86%, and the molar percentage content of the Mn3O4 phase oxide is 14% based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 77.08%, and the temperature corresponding to the maximum conversion rate of NO is 260.2°C.

[0142] Example 21

[0143] A certain volume of liquid salt solution of platinum nitrate is taken according to the loading amount of 0.30wt%Pt, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.20 La 0.02 Nd 0.03 Y 0.03 Mn 0.20 Zr 0.50 Cu 0.02 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 86%, and the molar percentage content of the Mn3O4 phase oxide is 14% based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 77.08%, and the temperature corresponding to the maximum conversion rate of NO is 260.2°C. 0.20 La 0.02 Nd 0.03 Y0.03 Mn 0.20 Zr 0.50 Cu 0.02 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 75%, the molar percentage content of the Mn3O4 phase oxide is 24%, and the molar percentage content of other manganese oxide phases is 1%, based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 62.08%, and the temperature corresponding to the maximum conversion rate of NO is 351.6°C.

[0144] Example 22

[0145] A certain volume of platinum chloride liquid salt solution is taken in an amount of 0.18wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.10 Nd 0.05 Y 0.05 Mn 0.15 Zr 0.50 Cu 0.15 O2slurry, and dried at a temperature of 80°C for 8h, and then high-temperature heat treated at 550°C for 5h, and calcined at 600°C under H2atmosphere for 3h, to obtain 0.18wt% Pt / Ce 0.10 Nd 0.05 Y 0.05 Mn 0.15 Zr 0.50 Cu 0.15 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 75%, the molar percentage content of the Mn3O4 phase oxide is 24%, and the molar percentage content of other manganese oxide phases is 1%, based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 62.08%, and the temperature corresponding to the maximum conversion rate of NO is 351.6°C.

[0146] Example 23

[0147] A certain volume of platinum nitrate liquid salt solution is taken in an amount of 0.01wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.05 Nd 0.05 Y 0.05 Mn 0.20 Zr 0.70 Al 0.10 O2slurry, and dried at a temperature of 60°C for 24h, and then high-temperature heat treated at 900°C for 2h, and calcined at 450°C under O2atmosphere for 6h, to obtain 0.01wt% Pt / Ce 0.05 Nd 0.05 Y 0.05 Mn 0.20 Zr 0.70 Al 0.10O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide is 74.9%, the molar percentage content of the Mn3O4 phase oxide is 25%, and the molar percentage content of other manganese oxide phases is 0.1%, calculated based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 54.71%, and the temperature corresponding to the maximum conversion rate of NO is 364.3°C.

[0148] Example 24

[0149] A certain volume of liquid salt solution of platinum nitrate is taken in an amount of 0.18wt% Rh loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.05 Nd 0.05 Mn 0.05 Zr 0.80 O2 slurry, and dried at a temperature of 140°C for 8h, and then high-temperature heat treated at 700°C for 3h, and calcined at 800°C for 1h in an Ar atmosphere, to obtain 0.18wt% Rh / Ce 0.05 Nd 0.05 Mn 0.05 Zr 0.80 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide is 74.9%, the molar percentage content of the Mn3O4 phase oxide is 25%, and the molar percentage content of other manganese oxide phases is 0.1%, calculated based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 54.71%, and the temperature corresponding to the maximum conversion rate of NO is 364.3°C.

[0150] Example 25

[0151] A certain volume of liquid salt solution of diethanolamine hexahydroxyplatinum acid is taken in an amount of 0.18wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.20 La 0.10 Mn 0.20 Zr 0.50 O2 slurry, and dried at a temperature of 120°C for 8h, and then high-temperature heat treated at 600°C for 2h, and calcined at 550°C for 3h in a CO atmosphere, to obtain 0.18wt% Pt / Ce 0.20 La 0.10 Mn 0.20 Zr 0.50 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide is 74.9%, the molar percentage content of the Mn3O4 phase oxide is 25%, and the molar percentage content of other manganese oxide phases is 0.1%, calculated based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 54.71%, and the temperature corresponding to the maximum conversion rate of NO is 364.3°C.

[0152] Example 26

[0153] A certain volume of liquid platinum nitrate salt solution was taken in an amount of 0.18wt% Pt loading, and mixed with the rare earth manganese zirconium composite oxide Ce 0.20 La 0.05 Nd 0.05 Mn 0.20 Zr 0.50 O 1.98 P 0.01 The slurry was mixed uniformly, dried at a temperature of 80°C for 12h, then high-temperature heat treated at 600°C for 2h, and calcined at 500°C for 4h in a CO atmosphere to obtain 0.18wt% Pt / Ce 0.20 La 0.05 Nd 0.05 Mn 0.20 Zr 0.50 O 1.98 P 0.01 . Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 87%, the molar percentage content of the Mn3O4 phase oxide was 12.5%, and the molar percentage content of other manganese oxide phases was 0.5% based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 85.04%, and the temperature corresponding to the maximum conversion rate of NO was 234.7°C.

[0154] Example 27

[0155] A certain volume of liquid platinum nitrate salt solution was taken in an amount of 0.18wt% Pt loading, and mixed with the rare earth manganese zirconium composite oxide Ce 0.15 Nd 0.05 Mn 0.05 Zr 0.65 V 0.05 Sn 0.05 O2The slurry was mixed uniformly, dried at a temperature of 150°C for 5h, then high-temperature heat treated at 300°C for 5h, and calcined at 850°C for 1h in a CO atmosphere to obtain 0.18wt% Pt / Ce 0.15 Nd 0.05 Mn 0.05 Zr 0.65 V 0.05 Sn 0.05 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 88%, and the molar percentage content of the Mn3O4 phase oxide was 12% based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 72.13%, and the temperature corresponding to the maximum conversion rate of NO was 274.8°C.

[0156] Example 28

[0157] A certain volume of liquid salt solution of platinum nitrate and palladium nitrate was taken in the loading amount of 0.15wt% Pd and 0.03wt% Pt, and was mixed with the rare earth manganese zirconium composite oxide Ce 0.25 La 0.05 Y 0.05 Mn 0.15 Zr 0.40 Zn 0.10 O2was mixed uniformly, and was dried at a temperature of 150°C for 5h, and then was high-temperature heat treated at 500°C for 4h, and was calcined at 800°C for 6h in a H2atmosphere, to obtain 0.18wt% PtPd / Ce 0.25 La 0.05 Y 0.05 Mn 0.15 Zr 0. 40 Zn 0.10 O2. Among them, the molar percentage content of the mullite type REMn2O5phase oxide was 74.2%, the molar percentage content of the Mn3O4phase oxide was 25%, and the molar percentage content of other manganese oxide phases was 0.8%, calculated on the basis of the manganese oxide phase. The above sample was tested for catalytic performance, and the maximum conversion rate of NO was 64.83%, and the temperature corresponding to the maximum conversion rate of NO was 301.4°C.

[0158] Example 29

[0159] A certain volume of liquid salt solution of platinum nitrate and rhodium nitrate was taken in the loading amount of 0.15wt% Pt and 0.03wt% Rh, and was mixed with the rare earth manganese zirconium composite oxide Ce 0.10 La 0.05 Nd 0.05 Pr 0.20 Mn 0.30 Zr 0.20 O2was mixed uniformly, and was dried at a temperature of 120°C for 4h, and then was high-temperature heat treated at 550°C for 3h, and was calcined at 450°C for 6h in a CO atmosphere, to obtain 0.18wt% PtRh / Ce 0.10 La 0.05 Nd 0.05 Pr 0.20 Mn 0.30 Zr 0.20 O2. Among them, the molar percentage content of the mullite type REMn2O5phase oxide was 78%, the molar percentage content of the Mn3O4phase oxide was 21.6%, and the molar percentage content of other manganese oxide phases was 0.4%, calculated on the basis of the manganese oxide phase. The above sample was tested for catalytic performance, and the maximum conversion rate of NO was 83.77%, and the temperature corresponding to the maximum conversion rate of NO was 302.8°C.

[0160] Example 30

[0161] A certain volume of liquid salt solution of platinum nitrate was taken in an amount of 0.18wt% Pt loading, and mixed with the rare earth manganese zirconium composite oxide Ce 0.10 Mn 0.15 Zr 0.70 Fe 0.05 O2The slurry was mixed uniformly, dried at a temperature of 140°C for 3h, then high-temperature heat treated at 550°C for 4h, and calcined at 600°C for 2h in a CO2atmosphere to obtain 0.18wt% Pt / Ce 0.10 Mn 0.15 Zr 0.70 Fe 0.05 O2. Among them, the molar percentage content of the mullite-type REMn2O5phase oxide was 83%, and the molar percentage content of the Mn3O4phase oxide was 17%, calculated based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 64.22%, and the temperature corresponding to the maximum conversion rate of NO was 348.1°C.

[0162] Example 31

[0163] A certain volume of liquid salt solution of platinum nitrate was taken in an amount of 0.18wt% Pt loading, and mixed with the rare earth manganese zirconium composite oxide Ce 0.15 La 0.05 Y 0.05 Mn 0.20 Zr 0.50 Al 0.05 O 1.98 P 0.01 The slurry was mixed uniformly, dried at a temperature of 180°C for 0.5h, then high-temperature heat treated at 450°C for 3h, and calcined at 500°C for 12h in a CO atmosphere to obtain 0.18wt% Pt / Ce 0.15 La 0.05 Y 0.05 Mn 0.20 Zr 0.50 Al 0.05 O 1.98 P 0.01 . Among them, the molar percentage content of the mullite-type REMn2O5phase oxide was 74%, the molar percentage content of the Mn3O4phase oxide was 25%, and the molar percentage content of other manganese oxide phases was 1%, calculated based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 70.68%, and the temperature corresponding to the maximum conversion rate of NO was 284.5°C.

[0164] Example 32

[0165] A certain volume of liquid salt solution of platinum nitrate and palladium nitrate was taken in an amount of 0.12wt% Pd and 0.06wt% Pt loading, and mixed with the rare earth manganese zirconium composite oxide Ce 0.15 Nd 0.05 Pr0.05 Eu 0.05 Mn 0.20 Zr 0.50 O2was mixed uniformly, dried at 100°C for 6h, then high temperature heat treated at 600°C for 2h, and calcined at 900°C for 2h under H2atmosphere to obtain 0.18wt% PtPd / Ce 0.15 Nd 0.05 Pr 0.05 Eu 0.05 Mn 0.20 Zr 0.50 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 74%, the molar percentage content of the Mn3O4 phase oxide is 24.5%, and the molar percentage content of other manganese oxide phases is 1.5%, calculated based on the manganese oxide phase. The above sample was tested for catalytic performance, and the maximum conversion rate of NO was 48.44%, and the temperature corresponding to the maximum conversion rate of NO was 406.7°C.

[0166] Example 33

[0167] A certain volume of liquid salt solutions of platinum nitrate and rhodium nitrate was taken according to the loading amount of 0.12wt% Pt and 0.06wt% Rh, and mixed with the rare earth manganese zirconium composite oxide Ce 0.20 La 0.05 Nd 0.05 Mn 0.20 Zr 0.20 W 0.20 O2was mixed uniformly, dried at 80°C for 12h, then high temperature heat treated at 550°C for 4h, and calcined at 900°C for 2h under CO atmosphere to obtain 0.18wt% PtRh / Ce 0.20 La 0.05 Nd 0.05 Mn 0.20 Zr 0.20 W 0.20 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 91.3%, the molar percentage content of the Mn3O4 phase oxide is 7.7%, and the molar percentage content of other manganese oxide phases is 1%, calculated based on the manganese oxide phase. The above sample was tested for catalytic performance, and the maximum conversion rate of NO was 61.41%, and the temperature corresponding to the maximum conversion rate of NO was 365.3°C.

[0168] Example 34

[0169] A certain volume of liquid salt solutions of palladium nitrate, platinum nitrate and rhodium nitrate was taken according to the loading amount of 0.03wt% Pd, 0.12wt% Pt and 0.03wt% Rh, and mixed with the rare earth manganese zirconium composite oxide Ce 0.20 La 0.02 Nd 0.03 Y0.02 Mn 0.20 Zr 0.50 Hf 0.03 The O2 slurry was mixed uniformly, dried at 160°C for 1 h, then high-temperature heat treated at 400°C for 5 h, and calcined at 500°C for 6 h in a water vapor atmosphere to obtain 0.18wt% Pt Pd Rh / Ce 0.20 La 0.02 Nd 0.03 Y 0.02 Mn 0.20 Zr 0.50 Hf 0.03 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 86.5%, the molar percentage content of the Mn3O4 phase oxide was 12.5%, and the molar percentage content of other manganese oxide phases was 1%, based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 78.17%, and the temperature corresponding to the maximum conversion rate of NO was 301.4°C.

[0170] Example 35

[0171] A certain volume of a liquid salt solution of platinum nitrate was taken in an amount of 0.18wt% Pd loading, and mixed with a rare earth manganese zirconium composite oxide Ce 0.05 Y 0.05 Mn 0.20 Zr 0.70 O2 slurry was mixed uniformly, dried at 200°C for 2 h, then high-temperature heat treated at 600°C for 4 h, and calcined at 850°C for 7 h in an air atmosphere to obtain 0.18wt% Pt / Ce 0.05 Y 0.05 Mn 0.20 Zr 0.70 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 75%, the molar percentage content of the Mn3O4 phase oxide was 23.5%, and the molar percentage content of other manganese oxide phases was 1.5%, based on the manganese oxide phase. The above sample was subjected to catalytic performance testing, and the maximum conversion rate of NO was 58.76%, and the temperature corresponding to the maximum conversion rate of NO was 364.9°C.

[0172] Example 36

[0173] A certain volume of a liquid salt solution of 2-hydroxyethylammonium hexahydroxoplatinum was taken in an amount of 0.18wt% Pt loading, and mixed with a rare earth manganese zirconium composite oxide Ce 0.10 Mn 0.10 Zr 0.60 Zn 0.10 Al 0.10The O2 slurry was mixed uniformly, dried at 150°C for 5h, then high-temperature heat treated at 500°C for 4h, and calcined at 650°C for 12h in a CO atmosphere to obtain 0.18wt% Pt / Ce 0.10 Mn 0.10 Zr 0.60 Zn 0.10 Al 0.10 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 66%, and the molar percentage content of the Mn3O4 phase oxide was 34%, based on the manganese oxide phase. The above sample was subjected to catalytic performance test, and the maximum conversion rate of NO was 63.01%, and the temperature corresponding to the maximum conversion rate of NO was 333.8°C.

[0174] Example 37

[0175] A certain volume of liquid salt solution of palladium nitrate, platinum nitrate and rhodium nitrate was taken according to the loading amount of 0.03wt% Pd, 0.09wt% Pt and 0.06wt% Rh, and mixed with the rare earth manganese zirconium composite oxide Ce 0.20 La 0.05 Y 0. 05 Mn 0.20 Zr 0.50 O2 slurry was mixed uniformly, dried at 120°C for 6h, then high-temperature heat treated at 450°C for 5h, and calcined at 900°C for 6h in a water vapor atmosphere to obtain 0.18wt% PtPdRh / Ce 0. 20 La 0.05 Y 0.05 Mn 0.20 Zr 0.50 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide was 94%, the molar percentage content of the Mn3O4 phase oxide was 5%, and the molar percentage content of other manganese oxide phases was 1%. The above sample was subjected to catalytic performance test, and the maximum conversion rate of NO was 73.89%, and the temperature corresponding to the maximum conversion rate of NO was 312.3°C.

[0176] Example 38

[0177] A certain volume of liquid salt solution of palladium nitrate was taken according to the loading amount of 0.18wt% Pt, and mixed with the rare earth manganese zirconium composite oxide Ce 0.14 La 0.03 Nd 0.04 Y 0.05 Mn 0.16 Zr 0.58 O2 slurry was mixed uniformly, dried at 150°C for 5h, then high-temperature heat treated at 500°C for 4h, and calcined at 750°C for 2h in a CO atmosphere to obtain 0.18wt% Pt / Ce0.14 La 0.03 Nd 0.04 Y 0.05 Mn 0.16 Zr 0.58 O2. Among the manganese oxide phases, the molar percentage content of the mullite-type REMn205phase oxide is 60%, the molar percentage content of the Mn304phase oxide is 38%, and the molar percentage content of other manganese oxide phases is 2%. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 76.65%, and the temperature corresponding to the maximum conversion rate of NO is 267.3°C.

[0178] Example 39

[0179] A certain volume of platinum nitrate liquid salt solution is taken in an amount of 0.18wt% Pt loading, mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.20 Mn 0.05 Zr 0.55 Cr 0.10 Al 0.10 O2slurry, and dried at a temperature of 100°C for 10h, and then high-temperature heat treated at 450°C for 6h, and calcined at 750°C for 10h in a H2atmosphere, to obtain 0.18wt% Pt / Ce 0.20 Mn 0.05 Zr 0.55 Cr 0.10 Al 0.10 O2. Among the manganese oxide phases, the molar percentage content of the mullite-type REMn205phase oxide is 82%, the molar percentage content of the Mn304phase oxide is 16%, and the molar percentage content of other manganese oxide phases is 2%. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 61.76%, and the temperature corresponding to the maximum conversion rate of NO is 334.7°C.

[0180] Example 40

[0181] A certain volume of platinum nitrate liquid salt solution is taken in an amount of 0.05wt% Pt loading, mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.15 La 0.05 Nd 0.05 Y 0.05 Mn 0.15 Zr 0.55 O2slurry, and dried at a temperature of 800°C for 20h, and then high-temperature heat treated at 800°C for 2h, and calcined at 500°C for 6h in a N2atmosphere, to obtain 0.05wt% Pt / Ce 0.15 La 0.05 Nd 0.05 Y 0.05 Mn 0.15 Zr 0.55O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide is 89%, the molar percentage content of the Mn3O4 phase oxide is 10%, and the molar percentage content of other manganese oxide phases is 1%, based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 57.43%, and the temperature corresponding to the maximum conversion rate of NO is 345.3°C.

[0182] Example 41

[0183] A certain volume of liquid salt solution of palladium nitrate, platinum nitrate and rhodium nitrate is taken according to the loading amount of 0.06wt%Pd, 0.09wt%Pt and 0.03wt%Rh, and mixed with the rare earth manganese zirconium composite oxide Ce 0.20 La 0.05 Y 0. 05 Mn 0.20 Zr 0.50 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide is 89%, the molar percentage content of the Mn3O4 phase oxide is 10%, and the molar percentage content of other manganese oxide phases is 1%, based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 57.43%, and the temperature corresponding to the maximum conversion rate of NO is 345.3°C. 0.20 La 0.05 Y 0.05 Mn 0.20 Zr 0.50 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide is 89%, the molar percentage content of the Mn3O4 phase oxide is 10%, and the molar percentage content of other manganese oxide phases is 1%, based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 57.43%, and the temperature corresponding to the maximum conversion rate of NO is 345.3°C.

[0184] Example 41

[0185] A certain volume of liquid salt solution of palladium nitrate, platinum nitrate and rhodium nitrate is taken according to the loading amount of 0.06wt%Pd, 0.09wt%Pt and 0.03wt%Rh, and mixed with the rare earth manganese zirconium composite oxide Ce 0.20 Sm 0.20 La 0.02 Nd 0.05 Y 0.03 Mn 0.30 Zr 0.20 O2. Among them, the molar percentage content of the mullite-type REMn2O5 phase oxide is 89%, the molar percentage content of the Mn3O4 phase oxide is 10%, and the molar percentage content of other manganese oxide phases is 1%, based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 57.43%, and the temperature corresponding to the maximum conversion rate of NO is 345.3°C. 0.20 Sm 0.20 La 0.02 Nd 0.05 Y 0.03 Mn 0.30 Zr 0.20O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 86%, the molar percentage content of the Mn3O4 phase oxide is 12.5%, and the molar percentage content of other manganese oxide phases is 1.5% based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 60.03%, and the temperature corresponding to the maximum conversion rate of NO is 361.5°C.

[0186] Example 43

[0187] A certain volume of liquid salt solution of platinum nitrate is taken in an amount of 0.18wt% Pt loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.20 Sm 0.20 La 0.02 Nd 0.05 Y 0.03 Mn 0.30 Zr 0.20 O2 slurry is mixed uniformly, dried at a temperature of 120°C for 5h, then high-temperature heat treated at 500°C for 4h, calcined at 400°C for 7h in a CO2 atmosphere, to obtain 0.18wt% Pt / Ce 0.20 Sm 0.20 La 0.02 Nd 0.05 Y 0.03 Mn 0.30 Zr 0.20 O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 86%, the molar percentage content of the Mn3O4 phase oxide is 12.5%, and the molar percentage content of other manganese oxide phases is 1.5% based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum conversion rate of NO is 60.03%, and the temperature corresponding to the maximum conversion rate of NO is 361.5°C.

[0188] Example 44

[0189] A certain volume of liquid salt solution of palladium nitrate, platinum nitrate and rhodium nitrate is taken in an amount of 0.12wt% Pd, 0.03wt% Pt and 0.03wt% Rh loading, and mixed uniformly with the rare earth manganese zirconium composite oxide Ce 0.05 Nd 0.05 Mn 0.05 Zr 0.80 O2 slurry is mixed uniformly, dried at a temperature of 100°C for 2h, then high-temperature heat treated at 450°C for 3h, calcined at 250°C for 12h in a water vapor atmosphere, to obtain 0.18wt% PtPdRh / Ce 0.05 Nd 0.05 Mn 0.05 Zr 0.80O2. Among them, the molar percentage content of the mullite type REMn2O5 phase oxide is 95%, the molar percentage content of the Mn3O4 phase oxide is 3%, and the molar percentage content of other manganese oxide phases is 2% based on the manganese oxide phase. The above sample is subjected to catalytic performance test, and the maximum NO conversion rate is 68.89%, and the temperature corresponding to the maximum NO conversion rate is 342.3°C.

[0190] The specific conditions, parameters and test results of the embodiments are shown in Table 2.

[0191] Table 2

[0192] From the data of the above comparative examples and embodiments, it can be seen that the maximum NO conversion rate of the aluminum-based noble metal catalytic material in the comparative examples and the rare earth manganese zirconium composite oxide without loading noble metal is less than 65%, wherein the conversion temperature corresponding to the highest NO conversion rate of the comparative example without pretreatment is above 340°C, the highest NO conversion rate of the rare earth manganese zirconium composite compound obtained by the preparation method of each embodiment of the present application is 85.51%, and the conversion temperature corresponding to the highest conversion rate is 231.3°C. The NO conversion rate is obviously improved, and the corresponding conversion temperature is obviously reduced, and obvious beneficial technical effects are achieved.

[0193] In addition, the catalytic performance test is as follows: 100 mg of the prepared rare earth manganese zirconium composite compound is placed in a microreactor for catalyst activity evaluation test, and the contents of NO, NO2 and NOx at the corresponding temperature are recorded by an infrared gas analyzer (MKS), so as to calculate the conversion rate of NO. The specific test conditions are as follows: the volume composition of the reaction gas is 10% oxygen, 500 ppm carbon monoxide, 500 ppm nitric oxide, 300 ppm hydrocarbon, and the balance is nitrogen, and the space velocity is 80000 h -1 .

[0194] The active site detection method is as follows: the vibration frequency and intensity of the probe molecule (such as CO) are closely related to the electronic and coordination structure of the catalytic metal site, which can effectively characterize the dispersion state and electronic valence state of the metal particles in the supported metal catalyst, help to study the active center of the catalyst, explore the adsorption behavior of the reactants, and deeply understand the reaction mechanism. DRIFTS test is carried out on a Thermo Nicolet iS50 FTIR spectrometer and a Praying Mantis high temperature reaction chamber. CO adsorption on various samples is measured at room temperature, CO is used as a probe molecule, and pure CO is introduced into the DRIFTS chamber at a flow rate of 10 ml min -1 . -1The flow rate of the gas phase CO in the chamber is purged by He to remove the gas phase CO in the chamber. The same method is used to test the NO adsorption on each sample. X-ray photoelectron spectroscopy (XPS) is used to analyze the noble metal valence state composition, and transmission electron microscopy is used to observe and analyze the particle size distribution of the noble metal and the rare earth manganese zirconium composite oxide.

[0195] Accordingly, a third aspect of the embodiments of the present application provides a catalyst comprising the noble metal supported rare earth manganese zirconium composite catalytic material described above, which is applied to motor vehicle exhaust purification, industrial organic waste gas treatment, natural gas catalytic combustion, petrochemical industry, hydrogen energy and battery fields.

[0196] The embodiments of the present application aim to protect a noble metal supported rare earth manganese zirconium composite catalytic material and a preparation method and a catalyst thereof. a Mn b Zr c L d O (2-δ) D β , and the chemical general formula is P / RE a Mn b Zr c L d O (2-δ) D β The catalytic material has double active sites, which are P species active sites and rare earth manganese composite species active sites; RE is a rare earth element, L is a cation-doped element, D is an anion-doped element, P is a platinum group metal element, 0.1≤a≤0.5, 0.05≤b≤0.3, 0.2≤c≤0.8, 0≤d≤0.2, 0≤δ≤0.1, 0≤β≤0.1, and a+b+c+d=1. The above technical solution has the following effects:

[0197] By constructing the composite catalytic material twice, the interaction between the metal and the composite carrier is regulated, the different bonding strengths of the surface noble metal active species and the active composite rare earth manganese zirconium are obtained, and the composite catalytic material with double active sites and high efficiency synergistic effect is obtained. δ+ -O-Mn γ+ , Pt δ+ -O-RE γ+ bond, to improve the NO low-temperature catalytic oxidation capacity, broaden the NO oxidation window, improve the high-temperature stability and durability of the DOC material, and at the same time improve the noble metal utilization rate and reduce the cost of the catalytic material.

[0198] It should be understood that the foregoing detailed description of the application, rather than limiting the application, is intended to explain and describe the current implementation of the application. Therefore, any modification, equivalent replacement or improvement made without departing from the spirit and scope of the application should be included in the protection scope of the application. In addition, the appended claims of the application are intended to cover all changes and modifications falling within the scope and boundary of the appended claims, or the equivalent form of such scope and boundary.

Claims

1. A noble metal supported rare earth manganese zirconium composite catalytic material, characterized in that, The catalytic material comprises a noble metal P and a rare earth manganese zirconium composite oxide RE a Mn b Zr c L d O (2-δ) D β , and a chemical general formula of P / RE a Mn b Zr c L d O (2-δ) D β , and the catalytic material has double active sites, which are a P species active site and a rare earth manganese composite species active site; Wherein, RE is a rare earth element, L is a cation-doped element, D is an anion-doped element, P is a platinum group metal element, 0.1≤a≤0.5, 0.05≤b≤0.3, 0.2≤c≤0.8, 0≤d≤0.2, 0≤δ≤0.1, 0≤β≤0.1, and a+b+c+d=1.

2. The noble metal supported rare earth manganese zirconium composite catalytic material according to claim 1, characterized in that, The P species include at least one of a metallic state and / or different valence oxidation states of the noble metal. 3.The noble metal supported rare earth manganese zirconium composite catalytic material according to claim 1, wherein the rare earth manganese composite species include at least one of a mullite type REMn 2O 5, a perovskite type REMnO 3, Mn 3O 4, Mn 2O 3, MnO, MnO 2 and an amorphous rare earth manganese oxide species. 4.The noble metal supported rare earth manganese zirconium composite catalytic material according to claim 3, wherein the rare earth manganese composite species include a mullite type REMn 2O 5 and Mn 3O 4. 5.The noble metal supported rare earth manganese zirconium composite catalytic material according to claim 4, wherein the molar percentage content of the mullite type REMn 2O 5 phase oxide is 60.0% to 97.0%, the molar percentage content of the Mn 3O 4 phase oxide is 3.0% to 38.0%, and the molar percentage content of other manganese oxide phases is 0 to 2.0%. 6.The noble metal supported rare earth manganese zirconium composite catalytic material according to claim 4, wherein the other manganese oxide phases include one or a combination of one or more of a perovskite phase REMnO 3, a MnO phase, a Mn 2O 3 phase and a MnO 2 phase. 7.The noble metal supported rare earth manganese zirconium composite catalytic material according to claim 1, wherein the primary particle size of the noble metal P is 0.1nm to 5nm, preferably 1nm to 3nm. 8.The noble metal supported rare earth manganese zirconium composite catalytic material according to claim 2, wherein the loading of the noble metal P is 0.01% to 0.3% by mass, preferably 0.05% to 0.2%; and the proportion of the metallic state in the noble metal P is 15% to 85%, preferably 35% to 65%. 9.The noble metal supported rare earth manganese zirconium composite catalytic material according to claim 1, wherein the noble metal P includes at least one of a platinum group metal Pt, Pd, Rh, Ir, Os and Ru, preferably at least one of Pt, Pd and Rh. 10.The noble metal supported rare earth manganese zirconium composite catalytic material according to any one of claims 1 to 9, wherein the rare earth manganese zirconium composite oxide is prepared by a method comprising the following steps: ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ The rare earth element RE includes at least one of La, Ce, Pr, Nd, Sm, Eu, Gd, Yb and Y; The doping element L includes at least one of transition metal elements, alkaline earth metal elements and Al, Si, Sn, preferably at least one of Fe, Co, Ni, Cu, Zn, V, Ti, Cr, Mo, W, Sn, Nb, Al, Si, Ga, Ge, In, Hf, Ba, Sr, Mg and Ca; The doping element D includes at least one of anions N, P, F and S.

11. A method for preparing a noble metal supported rare earth manganese zirconium composite catalytic material, characterized in that, The preparation method of the precious metal supported rare earth manganese zirconium composite catalytic material according to any one of claims 1-10 comprises the following steps: The compound of the precious metal P is ultrasonically dispersed into a preset solvent to obtain a compound solution of the precious metal P, wherein the preset solvent includes at least one of deionized water, ethanol and acetone; The compound solution of the noble metal P is added to the slurry containing the rare earth manganese zirconium composite catalyst RE a Mn b Zr c L d O (2-δ) D β , dried and calcined to produce P / RE a Mn b Zr c L d O (2-δ) D β precursor; P / RE a Mn b Zr c L d O (2-δ) D β The precursor is heat-treated under a preset atmosphere condition to obtain P / RE a Mn b Zr c L d O (2-δ) D β The finished product.

12. The method for preparing the noble metal-supported rare earth manganese-zirconium composite catalytic material according to claim 11, characterized in that, Before the compound of the precious metal P is ultrasonically dispersed into the preset solvent, the method further comprises: The salt solution of all the zirconium, all the RE and all the cationic doping element L is mixed, and an alkaline substance is added for a precipitation reaction, and after filtration, washing, drying and calcination, a rare earth zirconium oxide containing RE and L is obtained; The salt solution of all the manganese, the remaining RE and / or the remaining cationic doping element L is mixed with the rare earth zirconium oxide in one or more steps to obtain a composite compound precursor, wherein the multiple steps refer to the step-by-step addition of manganese; After heat treatment of the composite compound precursor, a rare earth manganese zirconium composite catalyst RE a Mn b Zr c L d O (2-δ) D β .

13. The method for preparing the noble metal-supported rare earth manganese-zirconium composite catalytic material according to claim 11, characterized in that, Before the compound of the precious metal P is ultrasonically dispersed into the preset solvent, the method further comprises: The salt solution of all the zirconium, part of the RE and / or part of the cationic doping element L is mixed, and an alkaline substance is added for a precipitation reaction, and after filtration, washing, drying and calcination, a rare earth zirconium oxide containing RE and L is obtained; The salt solution of all the manganese, the remaining RE and / or the remaining cationic doping element L is mixed with the rare earth zirconium oxide in one or more steps to obtain a composite compound precursor, wherein the multiple steps refer to the step-by-step addition of manganese; After heat treatment of the composite compound precursor, a rare earth manganese zirconium composite catalyst RE a Mn b Zr c L d O (2-δ) D β .

14. The preparation method of the precious metal supported rare earth manganese zirconium composite catalytic material according to claim 12 or 13, wherein The drying process temperature after the precipitation reaction is 60-200°C, preferably 80-180°C, and the drying process time is 1-24h, preferably 2-12h; The calcination process temperature after the precipitation reaction is 500-1000°C, preferably 600-900°C, and the calcination process time is 1-20h, preferably 2-10h; The heat treatment process temperature of the composite compound precursor is 100-1000°C, preferably 200-900°C, and the heat treatment time is 1-20h, preferably 3-10h.

15. The preparation method of the precious metal supported rare earth manganese zirconium composite catalytic material according to claim 11, wherein The compound of the precious metal P includes at least one of chloride, nitrate, acetate, 2-hydroxyethylammonium hexahydroxyl P, diethanolamine hexahydroxyl P and citrate aqueous solution.

16. The preparation method of the precious metal supported rare earth manganese zirconium composite catalytic material according to claim 11, wherein The drying process temperature of the slurry is 60-200℃, and the drying process time is 1-24h; The calcination process temperature of the slurry after drying treatment is 300-900℃, and the calcination process time is 2-12h; The heat treatment process temperature of the precursor under the preset atmosphere condition is 200-900℃, preferably 350-750℃; The heat treatment process time of the precursor under the preset atmosphere condition is 0.5-14h, preferably 3-10h.

17. The preparation method of the precious metal supported rare earth manganese zirconium composite catalytic material according to claim 11, characterized in that, The preset atmosphere condition comprises at least one of air, O2, CO, Ar, H2, CO2, N2 and water vapor.

18. A catalyst characterized by, The precious metal supported rare earth manganese zirconium composite catalytic material according to any one of claims 1-10 is applied to motor vehicle exhaust purification, industrial organic waste gas treatment, natural gas catalytic combustion, petrochemical industry, hydrogen energy and battery field.

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