PREPARATION AND PRETREATMENT TECHNIQUES OF CU/CEO2 CATALYSTS FOR LOW TEMPERATURE DIRECT DECOMPOSITION OF NOx

EXHAUST GAS CROS S REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No.

62/479,874, filed on March 31, 2017, the disclosure of which is hereby incorporated by reference.

FIELD OF THE DISCLOSURE

[0002] The present disclosure relates to the synthesis of copper-cerium oxide nanoparticles. More particularly, the disclosure relates to copper-cerium oxide nanoparticles that can be used as deNOx catalysts.

BACKGROUND OF THE DISCLOSURE

[0003] NOx exhaust gas, including NO, N2O and NO2, is a major pollutant gas emitted from automobiles and power plants using coal as fuel. NO remains to be a major environmental pollutant, which causes acid rain, photochemical smog and harmful effects on human health. The decomposition of NO is impeded with high activation energy barrier (around 150 kJ/mol), which requires high temperature for thermal NO decomposition. Hence, in order to decrease such high activation energy barrier with low energy consumption, it is necessary to develop efficient catalysts for direct NO decomposition at low temperature.

[0004] General catalytic elimination methods of NO include direct NO

decomposition, selective catalytic reduction, and NO storage and reduction. Both selective catalytic reduction (SCR) and NO storage, reduction need a reducing agent such as ammonia, hydrogen, hydrocarbons (HC) and urea, which are required to precise control over the stoichiometry. Additionally, these reducing agents can cause secondary pollution. In other words, the design of engine and emission control is more complex for selective catalytic reduction and NO storage, reduction. In contrast, direct NO decomposition is simple and environmental friendly way for NO decomposition since no co-reactant is not required.

[0005] Previous catalysts for direct NO decomposition have metal oxides, perovskite- type catalysts and zeolitic catalysts. Several transitional metal oxides have been studied to directly decompose NO, and among them C03O4 was one of the most active catalysts, while high temperature (above 600 °C) was required to obtain high NO conversion (above 80%). Perovskite-type catalysts with an ABO3 chemical composition contain certain amount of oxygen-deficient sites, which could absorb NO easily, so such catalysts also had good performance for NO decomposition. LaMn03 catalyst series, which usually were doped with other metals (Ba, Mn et al.) showed high activity for direct NO decomposition, and these catalysts could decompose NO by 80 % at 700 °C. Compare with the above oxide catalysts, Cu containing zeolitic catalysts, particularly CuZSM-5, were more active, due to contained specific active Cu dimmers. Prior studies reported CuZSM-5 with Si/Al ratio of 12 could decomposed NO by 80 % at 400 °C, which was much more active than reported oxide catalyst (Iwamoto et al. and Ishihara et al.).

[0006] The cold start of vehicles produces significant emission of pollutants. One such pollutant is NO _x . However, existing de-NOx catalysts are inactive at cold temperatures. Prior art NSR catalysts (e.g., Pt/BaO/Ah03) require temperatures in excess of 300 °C. Prior art SCR catalysts require a supply of reducing agent (e.g., urea) and temperatures in excess of 200 °C. See Figures 10-12.

[0007] Even though zeolite catalysts can directly decompose NO totally at around

450 °C, however, the total decomposition temperature for selective catalytic reduction method is as low as 150 °C to 250 °C, which still possesses advantage in energy

consumption. Therefore, in order to fully develop the advantage of direct NO decomposition, it is necessary to develop new catalysts, which can direct decompose NO at possible lower temperature.

SUMMARY OF THE DISCLOSURE

[0008] In an aspect, the present disclosure provides nanoparticles and compositions comprising nanoparticles. The nanoparticles can be used as catalysts. The nanoparticles can be made by a method of the present disclosure. In an example, a nanoparticle or nanoparticles are made by a method of the present disclosure. Various examples of nanoparticles and compositions are also referred to herein as copper doped cerium oxide nanoparticles and catalyst.

[0009] In an example, the present disclosure provides a Ce02 nanoparticle or nanoparticles having domains of one or more copper species (e.g., aqueous-insoluble copper(II) salts (e.g., copper carbonate), copper oxide, copper hydroxide, copper, and combinations thereof) and/or one or more alloy thereof disposed on at least a portion of a surface of the Ce02 nanoparticles. In another example, one or more of the copper domains comprise copper metal. [0010] In an aspect, the present disclosure provides methods of using the

nanoparticle/nanoparticles of the present disclosure. The nanoparticle/nanoparticles can be used as catalysts (in SCR and NSR reactions). For example, the nanoparticle/nanoparticles are used in methods of decomposing one or more nitrogen oxides. When describing different NO-based gases, NO _x and N _x O _y may be used interchangeably.

[0011] In an example, catalysts (e.g., nanoparticle(s) or materials) are synthesized in a precipitation method described herein followed by annealing. Catalysts were activated by hydrogen and helium thermal pretreatment. For example, under 300 °C, 5% Cu/CeC was capable of sustain 20 hours of nearly 100% conversion of NO exhaust gas with almost full selectivity to N ₂ . After deactivation, 5% Cu/Ce02 catalyst can be easily regenerated by Fh or CO. The addition of oxygen could reduce the lifetime of catalyst, but the catalyst also is able to be easily regenerated and shows desirable deNOx performance.

BRIEF DESCRIPTION OF THE FIGURES

[0012] For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures.

[0013] Figure 1 shows a preparation procedure and pretreatment method for Cu/Ce02 catalyst.

[0014] Figure 2 shows TEM images of commercial Ce02 and Cu precipitate Ce02 samples, a) Commercial Ce0 ₂ ; b) 2% Cu/Ce0 ₂ ; c) 5% Cu/Ce0 ₂ ; d) 8% Cu/Ce0 ₂ .

[0015] Figure 3 shows XRD data of commercial Ce0 ₂ and 2%, 5% and 8% Cu precipitate Ce02 samples, respectively.

[0016] Figure 4 shows an industrial design of deNOx process utilizing Cu/Ce02 catalyst.

[0017] Figure 5 shows catalytic reaction results of NO decomposition over commercial Ce02, 5% Cu/AhOs and 5% Cu/Ce02 catalysts at 30 °C.

[0018] Figure 6 shows catalytic reaction results of NO decomposition over 5%

Cu/Ce02 catalyst in the present disclosure at 30 °C and 300 °C.

[0019] Figure 7 shows catalytic reaction results of NO decomposition over 2% Cu/Ce02, 5% Cu/ Ce02, and 8% Cu/Ce02 catalysts in the present disclosure at 300 °C.

[0020] Figure 8 shows regeneration of 5% Cu/Ce02 catalyst by H ₂ reduction and catalytic NO decomposition results at 30 °C. [0021] Figure 9 shows regeneration of 5% Cu/CeC catalyst by H2 or CO reduction and catalytic NO decomposition results in presence of 5% O2 at 30 °C.

[0022] Figures 10, 1 1, and 12 show NOx conversion data for prior catalysts.

[0023] Figures 13-21 show various examples of use of nanoparticle(s) or materials of the present disclosure in deNOx methods.

[0024] Figure 22 shows XRD data. There is no peak for Cu, Pt, or Zr observed.

[0025] Figure 23 shows TEM micrographs. (A) CuCeOx. (B) CuPtCeOx. (C)

CuZrCe02. (D) Magnification of (C). Commercial Ce02 support is around 20 nm, CeZrOx is around 200 nm and CeZrOx has mesopores (including N2 adsorption-desorption results).

[0026] Figure 24 shows BET surface area of various catalysts. CuZrCeOx has the highest surface area.

[0027] Figure 25 shows NO storage and reduction (NSR) on CuCeOx. Lean gas is 500 ppm NO and 5% O2 and rich gas is 500 ppm NO + 1 % Hi.

[0028] Figure 26 shows NSR on CuCe0 ₂ . Lean gas is 500 ppm NO and 5% O2 and rich gas is 500 ppm NO + 1% CO.

[0029] Figure 27 shows deNOx ability in real vehicle exhaust by doping CeOx with Zr and adding Pt to Cu. At 100 °C, NO conversion on CuCeOx, CuPtCeOx, and CuZrCeOx were 33.3%, 43.3%, AND 53.7%.

[0030] Figure 28 shows a comparison of deNOx catalysts.

[0031] Figure 29 shows the deNOx activities of three way catalysts.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0032] Although claimed subject matter will be described in terms of certain embodiments, other embodiments, including embodiments that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. Various structural, logical, process step, and electronic changes may be made without departing from the scope of the disclosure.

[0033] Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include all values to the magnitude of the smallest value (either lower limit value or upper limit value) and ranges between the values of the stated range.

[0034] The present disclosure provides Cu/Ce02 nanoparticles, which can be used as deNOx catalysts, and preparation and pretreatment methods for same, and methods of use of the same. It further describes industrial design of catalytic processes and catalytic performance of the nanoparticles.

[0035] In an aspect, the present disclosure provides nanoparticles and compositions comprising nanoparticles. The nanoparticles can be used as catalysts. The nanoparticles can be made by a method of the present disclosure. In an example, a nanoparticle or nanoparticles are made by a method of the present disclosure. Various examples of nanoparticles and compositions are also referred to herein as copper doped cerium oxide nanoparticles and catalyst.

[0036] In an example, the present disclosure provides a CeCh nanoparticle or nanoparticles having domains of one or more copper species (e.g., aqueous-insoluble copper(II) salts (e.g., copper carbonate), copper oxide, copper hydroxide, copper, and combinations thereof) and/or one or more alloy thereof disposed on at least a portion of a surface of the CeCh nanoparticles. In another example, one or more of the copper domains comprise copper metal.

[0037] In an example, a material comprising one or more nanoparticles, wherein the nanoparticles are CeCh nanoparticles, which comprise one or more additional metals, having domains of one or more copper species (e.g., aqueous-insoluble copper(II) salts (e.g., copper carbonate), copper oxide, copper hydroxide, copper, and combinations thereof) and/or alloys thereof disposed on at least a portion of a surface of the CeCh nanoparticles. In another example, one or more of the copper domains comprise copper metal.

[0038] CeCh nanoparticles can have various compositions. A CeCh nanoparticle or nanoparticles can further comprise one or more additional metals (e.g., zirconium, zinc, magnesium, and combinations thereof). In various examples, the nanoparticle/nanoparticles is/are binary oxides such as, for example, Zr-Ce-O, Zn-Ce-O, and Mg-Ce-O. Suitable examples of CeCh nanoparticles can be made by methods known in the art and are commercially available.

[0039] Copper species are highly dispersed on CeCh nanoparticles. The copper species can be discrete domains. The size of copper species (e.g., domains of copper species) are subnanometer. The copper species can be alloys with one or more additional metals in varying amounts.

[0040] Copper (e.g., in an oxidized/ionic form and/or metallic form) can be present at various amounts in the nanoparticle/nanoparticles at various amounts. In various examples, copper is present at 0.001% by weight to 8% by weight, based on the total weight of the nanoparticle(s), including all values to 0.001% and ranges therebetween. In various other examples, copper is present at e.g., 2% by weight to 8% by weight or 4% by weight to 6% by weight, based on the total weight of the nanoparticle(s).

[0041] The nanoparticle/nanoparticles can comprise copper species that further comprise one or more additional non-copper metals. The one or more additional non-copper metals can be present as an alloy with the copper in the copper species. In various examples, the one or more additional non-copper metals is gold, silver, platinum, rhodium, palladium, iridium, rhodium, iron, cobalt, nickel, zirconium, or a combination thereof.

[0042] The nanoparticle/nanoparticles can be of various sizes. In various examples, the nanoparticle/nanoparticles has/have a longest dimension (e.g., diameter) or average longest dimension (e.g., average diameter) of 10 nm to 30 nm, including all integer nm values and ranges therebetween. Nanoparticle size can be measured by methods known in the art. For example, nanoparticle size is measured by microscopy methods (e.g., scanning electron microscopy (SEM) or transmission electron microscopy (TEM)) or light scattering methods (e.g., dynamic light scattering (DLS)).

[0043] The nanoparticle/nanoparticles can have various morphologies. In various examples, the nanoparticles is/are spherical or nanorods.

[0044] In an example, the nanoparticle/nanoparticles are subjected to

activation/pretreatment as described herein. The activated nanoparticle/nanoparticles have a Cu-Ce solid solution. The nanoparticle/nanoparticles have at least one active site (e.g., oxygen vacancy).

[0045] The nanoparticle/nanoparticles (e.g., nanoparticle/nanoparticles activated as described herein) can be used to catalyze various reactions. For example, the

nanoparticle/nanoparticles catalyzes a nitrogen oxide decomposition reaction (e.g., deN _x O _y reaction, wherein x and y are independently 1 or 2, but not simultaneously 2).

[0046] In an aspect, the present disclosure provides methods of making nanoparticles of the present disclosure. The methods are based on deposition of copper species on cerium oxide nanoparticles.

[0047] In various examples, a method of synthesizing nanoparticle/nanoparticles, which can be present in a material, comprises: a) adding (e.g., suspending) CeC (e.g., cerium oxide particles) in an aqueous medium (e.g., water such as, for example, deionized water); b) adding an aqueous-soluble copper salt (e.g., copper nitrate, copper chloride) to the aqueous medium from a) (e.g., CeCh suspension from a)) to form a mixture; c) adding an excess (e.g., molar excess based on the amount of copper present in the mixture) of a salt (e.g., a soluble salt) comprising an anion (e.g., carbonate anion, hydroxide ion) (e.g., sodium carbonate, sodium chloride) that forms an insoluble copper (e.g., copper(II)) salt to the mixture from b), wherein an insoluble copper (e.g., copper(II)) salt and/or copper hydroxide precipitates on at least a portion of a surface of at least a portion of the CeC (e.g., cerium oxide particles) to form a solid product material; d) isolating (e.g., by filtration) the solid product material from c); e) calcining (e.g., heating in air at 400 °C for 3 h (h = hour(s)) (heating ramp 2 °C/min)) the solid product material from d); and, optionally, f) graining the solid product from e) to form a material of any of the preceding claims.

[0048] Copper loading on CeCh can be manipulated by adding different amount of copper salt(s) (e.g., nitrate salt(s)) into the CeC -copper nitrate solution mixture. There was no observation on morphology change after copper precipitation.

[0049] The salt is present in an excess based on the amount of copper present in the mixture. Without intending to be limited by any particular theory, it is considered that that salt functions as a precipitant to ensure the Cu ions are captured and deposited on the surface of CeCh nanoparticles.

[0050] Optionally, the solid product from d) in the example above is grained.

Graining provides pellets (e.g., 40-60 mesh) of the solid product.

[0051] The solid product from d) can be subjected to conditions (e.g., pre such that an active catalyst material is provided.

[0052] In an aspect, the present disclosure provides methods of using the

nanoparticle/nanoparticles of the present disclosure. The nanoparticle/nanoparticles can be used as catalysts (in SCR and NSR reactions). For example, the nanoparticle/nanoparticles are used in methods of decomposing one or more nitrogen oxides. When describing different NO-based gases, NO _x and N _x O _y may be used interchangeably.

[0053] In an example, catalysts (e.g., nanoparticle(s) or materials) are synthesized in a precipitation method described herein followed by annealing. Catalysts were activated by hydrogen and helium thermal pretreatment. For example, under 300 °C, 5% Cu/CeC was capable of sustain 20 hours of nearly 100% conversion of NO exhaust gas with almost full selectivity to N ₂ . After deactivation, 5% Cu/Ce02 catalyst can be easily regenerated by Fh or CO. The addition of oxygen could reduce the lifetime of catalyst, but the catalyst also is able to be easily regenerated and shows desirable deNOx performance.

[0054] After the activation, the activated catalysts are able to catalyze deNOx reactions with nearly full conversion and 100% selectivity to N2 at ambient temperature (30 °C) for considerable amount of time (0.5 h to 20 h). [0055] In various examples, a method of decomposing one or more nitrogen oxides

(e.g., NxOy, wherein x and y are independently 1 or 2, but not simultaneously 2) using the nanoparticle/nanoparticles or material of the present disclosure comprises: a) contacting (e.g., flushing the atmosphere in which the material is present) nanoparticle(s) of the present disclosure or a material of the present disclosure or nanoparticle(s) or a material made by a method of the present disclosure with a gas comprising 0 to 10% ¾ (e.g., 0.001% by volume to 100% by volume, including all 0.001% values and ranges therebetween, or 0.001% by volume to 10% by volume) in an environment at a temperature of 150 °C to 800 °C, including all 0.001% values and ranges therebetween, (e.g., 300 °C to 500 °C); b) returning (e.g., cooling) the nanoparticle(s) or material from a) to room temperature (e.g., 18-25 °C); c) contacting the nanoparticle(s) or material from b) (e.g., flushing the atmosphere in which the nanoparticle(s) or material is/are present) with helium gas; d) heating the nanoparticle(s) or material from c) to a temperature of 150 °C to 800 °C, including all 0.001% values and ranges therebetween, (e.g., 300 °C to 500 °C); e) contacting the nanoparticle(s) or material from d) with the one or more nitrogen oxides (e.g., N _x O _y , wherein x and y are independently 1 or 2, but not simultaneously 2) at 150 °C to 800 °C, including all 0.001% values and ranges therebetween, (e.g., 30 °C to 300 °C), wherein at least a portion of the one or more nitrogen oxides (e.g., N _x O _y , wherein x and y are independently 1 or 2, but not simultaneously 2) are decomposed (e.g., to form nitrogen gas and oxygen gas).

[0056] Optionally, a method of decomposing one or more nitrogen oxides further comprises isolation of least a portion of the decomposed one or more nitrogen oxides from the nanoparticle(s) or material. The decomposed one or more nitrogen oxides can be isolated by methods known in the art.

[0057] Copper doped cerium oxide (Cu/CeC ) catalysts of the instant disclosure can be synthesized by precipitation methods described herein. Copper active sites are well dispersed on the surface of CeCh with a preparation method of the present disclosure. The nanoparticle(s) or materials have at least one active site (e.g., oxygen vacancy). The CeCh nanoparticles possess high oxygen storage capacity.

[0058] The as-prepared Cu/CeCh catalysts are capable of undergoing activation with hydrogen reduction and helium thermal pretreatment. After pretreatment (e.g., a)-d) in the method above), a Cu-Ce solid solution is formed. Without intending to be bound by any particular theory it is considered that the interface between Cu and Ce plays an important role in nitrogen oxide decomposition. [0059] Examples 5 and 6 show that the interface between Cu and CeC was created and synergistic effects between Cu and CeC not only had good capacity of NO

decomposition, but also was able to retard the deactivation of Cu/CeC . Without intending to be bound by any particular theory, it is considered that NO can be decomposed on the interface between Cu and Ce02, and then the left adsorbed oxygen intermediate after N2 release can be migrated to oxygen vacancies and recover active sites. Moreover, the migrated rate is expected to increase with increment of temperature, so the lifetime of Cu/Ce02 is expected to last for nearly 20 hours.

[0060] Comparison in Example 7 show that a desirable Cu loading of Cu/Ce02 is 5%. At too low Cu loading the Cu/Ce02 nanoparticle have an undesirable number of active sites and at too high a Cu loading, Cu sites were aggregated, which is not favored for NO decomposition.

[0061] The nanoparticle(s) or material can be regenerated and reused in a method.

Optionally, a method of decomposing one or more nitrogen oxides further comprises regeneration and, if desired, reuse of the regenerated nanoparticle(s) or material. In various examples, nanoparticle(s) or material previously used to decomposing one or more nitrogen oxides is contacted (e.g., a temperature of 300 °C to 800 °C for certain time (e.g., 0.5 h to 10 h) with a gas comprising hydrogen (e.g., a gas comprising 0.001% by volume to 100% by volume H2 gas (e.g., 5% H2 gas) or CO gas), where at least a portion of the copper in the material is reduced to copper metal. Examples 8 and 9 show that after deactivation, the catalyst can be regenerated. The activity and lifetime were able to recover on regeneration. In various examples, activity and/or lifetime values were recovered to 90% or greater, 95% or greater, or 99% or greater of their original values after regeneration.

[0062] A method can be carried out in various configurations. A method can be carried out as continuous process.

[0063] The steps of the methods described in the various embodiments and examples disclosed herein are sufficient to carry out the methods of the present disclosure. Thus, in various examples, a method consists essentially of a combination of the steps of the methods disclosed herein. In various other examples, a method consists of such steps.

[0064] The following Statements provide embodiments and/or examples of nanoparticles (e.g., Ce02 nanoparticles) having domains of one or more copper species, methods of the present disclosure (e.g., methods of making materials of the present disclosure), and articles of manufacture of the present disclosure (e.g., articles of manufacture comprising one or more layers of the present disclosure): Statement 1. A material comprising one or more nanoparticles, wherein the nanoparticles are CeCh nanoparticles having domains of one or more copper species (e.g., aqueous-insoluble copper(II) salts (e.g., copper carbonate), copper oxide, copper hydroxide, and combinations thereof) disposed on at least a portion of a surface of the CeCh nanoparticles.

Statement 2. The material of Statement 1, wherein the copper is present at 0.001% by weight to 8% by weight (e.g., 2% by weight to 8% by weight or 4% by weight to 6% by weight) based on the total weight of the nanoparticle(s).

Statement 3. The material of Statements 1 or 2, wherein the nanoparticles have a longest dimension (e.g., diameter) of 10 nm to 30 nm.

Statement 4. The material of any one of the preceding Statements, wherein the nanoparticles are spherical or nanorods.

Statement 5. The material of any one of the preceding Statements, wherein one or more of the copper species further comprise (e.g., as an alloy with the copper in the copper species) one or more additional non-copper metals (e.g., gold, silver, platinum, rhodium, palladium, zirconium, or a combination thereof).

Statement 6. The material of any of the preceding Statements, wherein the material catalyzes a nitrogen oxide decomposition reaction (e.g., deN _x O _y reaction, wherein x and y are independently 1 or 2, but not simultaneously 2).

Statement 7. A method of synthesizing a material of any one of the preceding Statements comprising:

a) adding (e.g., suspending) CeCh (e.g., cerium oxide particles) in an aqueous medium (e.g., water such as, for example, deionized water);

b) adding an aqueous-soluble copper salt (e.g., copper nitrate, copper chloride) to the aqueous medium from a) (e.g., CeCh suspension from a)) to form a mixture;

c) adding an excess of a salt (e.g., a soluble salt) comprising an anion (e.g., carbonate anion or hydroxide) (e.g., sodium carbonate, sodium hydroxide) that forms an insoluble copper (e.g., copper(II)) salt to the mixture from b), wherein an insoluble copper (e.g., copper(II)) salt and/or copper hydroxide precipitates on at least a portion of a surface of at least a portion of the Ce02 (e.g., cerium oxide particles) to form a solid product material;

d) isolating (e.g., by filtration) the solid product material from c); e) optionally, calcining (e.g., heating in air at, for example, 400 °C for 3 hours (heating ramp 2 °C/min)) the solid product material from d); and f) optionally, graining the solid product from e) to form a material of any of the preceding claims.

Statement 8. A method of decomposing one or more nitrogen oxides (e.g., N _x O _y , wherein x and y are independently 1 or 2, but not simultaneously 2) using the material of any one of claims 1-6 or a material made by the method of Statement 7:

a) contacting (e.g., flushing the atmosphere in which the material is present) the material of any one of Statements 1-4 or a material made by the method of Statement 5 with a gas comprising 0 to 10% H2 (e.g., 0.001% by volume to 100% by volume) in an environment at a temperature of 150 °C to 800 °C;

b) returning (e.g., cooling) the material from a) to room temperature (e.g., 18-

25 °C);

c) contacting the material from b) (e.g., flushing the atmosphere in which the material is present) with helium gas;

d) heating the material from c) to a temperature of 300 °C to 800 °C;

e) contacting the material from d) with the one or more nitrogen oxides (e.g.,

NxOy, wherein x and y are independently 1 or 2, but not simultaneously 2) at 30 °C to 800 °C, wherein at least a portion of the one or more nitrogen oxides (e.g., N _x O _y , wherein x and y are independently 1 or 2, but not simultaneously 2) are decomposed (e.g., to form nitrogen gas and oxygen gas).

Statement 9. The method of Statement 8, wherein the material of any of the preceding claims comprises nanoparticles having at least one active site (e.g., oxygen vacancy).

Statement 10. The material of Statement 9, wherein a plurality of active sites (e.g., subnanometer active sites) are highly dispersed (e.g., are discrete active sites) on the nanoparticles.

Statement 11. The method of any one of Statements 8-10, wherein at least a portion of the decomposed one or more nitrogen oxides (e.g., N _x O _y , wherein x and y are independently 1 or 2, but not simultaneously 2) are isolated from the material.

Statement 12. The method of any one of Statements 8-11, wherein the material from e) is contacted (e.g., at a temperature of 300 °C to 800 °C for certain time (e.g., 0.5 h to 10 h)) with a gas comprising hydrogen (e.g., a gas comprising 0.001% by volume to 100% by volume ¾ (e.g., 5% H2)) or CO gas, wherein at least a portion of the copper in the material is reduced to copper metal. Statement 13. The method of Statement 12, wherein the material from Statement 12 is used in b) in any one of claims 8-11.

Statement 14. The method of any one of Statements 8-13, wherein the method is carried out as a continuous process.

[0065] The following examples are presented to illustrate the present disclosure. They are not intended to limiting in any matter.

EXAMPLE 1

[0066] This example provides a description of synthesis and use of Cu/CeC catalysts of the present disclosure.

[0067] NOx exhaust gas, including NO, N2O and NO2, is a major pollutant gas emitted from automobiles and power plants using coal as fuel, which has caused severe environmental issues including acid rain and photochemical smog. At the condition of direct NOx decomposition, no reducing agent such as ammonia or hydrocarbons is required for the reduction of nitric oxide, which has been considered as the most applicable approach so far. The chemical formula for such reaction in the present disclosure can be represented as

2NO→N2+02. Direct NOx decomposition in an efficient deNOx pathway.

[0068] Direct NOx decomposition is achieved in the present disclosure by new hydrogen reduction and helium thermal pretreatment methods for activation of robust deNOx activity of 2wt% to 8wt% copper loading on ceria catalyst. Cu/Ce02 catalysts were prepared by precipitation of finely dispersed copper species over ceria nanoparticles. The obtained solid sample is calcined and grained. Under the hydrogen reduction and helium thermal treatment conditions of the present disclosure, catalysts are activated and exhibited effective deNOx ability. After deactivation, the Cu/Ce02 catalyst can be easily regenerated by H2 or CO. Even in the presence of O2, the Cu/Ce02 catalyst shows desirable deNOx performance.

[0069] In order to establish the catalytic activity of copper ceria catalysts, a series of tests were performed on direct NO and N2O reactions at temperatures from 30 °C to 300 °C, the catalytic reaction results were detected by Infrared Spectroscopy with fixed 5 m gas cell and Gas Chromatography-Barrier Ionization Discharge (GC-BID). The structures of the catalysts were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD).

[0070] Activity of the catalyst on deNOx reaction was tested at temperatures ranging from 30 °C to 300 °C for activating copper ceria catalysts under the condition of direct NOx decomposition, deNOx activity can be achieved as low as 30 °C. Under 300 °C, the prepared copper ceria catalysts, which underwent the above pretreatment method, can achieve full conversion of NO for about 20 hours. The deactivated catalyst can be reactivated by hydrogen or CO regeneration and reused in a deNOx reaction, even in the presence of O2.

[0071] The Cu/Ce02 catalysts were prepared via a precipitation method of different loadings (0 wt% to 8 wt%) of Cu on Ce02 nanoparticles, detailed results can be found in Figure 1. In a typical synthesis, Ce02 was mixed in water with copper nitrate, an excess amount of sodium carbonate was added to precipitate copper into copper carbonate. The solution was filtered to obtain solid product. The solid was calcined and grained. The catalysts were characterized by transmission electron micrograph (TEM) and X-ray

Diffraction (XRD). The characterization results showed sizes of support Ce02 nanoparticles were around 10 nm to 30 nm, and the Cu species were highly dispersed on Ce02. Detailed are shown in Figure 2 and Figure 3.

EXAMPLE 2 [0072] This example provides a description of pretreatment of Cu/Ce02 catalysts.

[0073] The catalyst pretreatment procedures in the present disclosure were carried out with hydrogen reduction followed by helium thermal treatment. In typical pretreatments, 0% to 10% hydrogen was flushed over the Cu/Ce02 catalyst at 300 °C to 500 °C. After Hi reduction, the temperature was cooled down to room temperature, pure helium gas was flushed over the catalyst to remove physical adsorbed H2, then increasing temperature to 300 °C to 500 °C to remove chemically adsorbed H2. Detailed results are shown in Figure 4.

EXAMPLE 3

[0074] This example provides a description of the catalytic reaction results of NO decomposition using different catalysts.

[0075] Catalytic reaction results of NO decomposition over commercial Ce02,

CU/AI2O3 and Cu/Ce02 series catalysts of the present disclosure can be compared in Figures 5 to 9 and described in following examples, respectively. In a typical reaction, 500 ppm NO gas is flushed over the activated catalyst with flowing rate at 20 ml/min in the packed bed. Conversion results were recorded by IR with a fixed 5 m gas cell and GC-BID. Summarized conversion and selectivity results can be viewed in Table 1.

Table 1 Direct NO decomposition on different catalysts pretreated by hydrogen reduction and subsequent helium thermal treatment at 500 °C Catalysts T (°C) ^a Time (mins) ^b Time (mins) ^c

Commercial CeC 30 30 8

CeC nanorods 30 250 200

5% Cu/Ce0 ₂ 30 450 450

5% Cu/Ce0 ₂ 300 1100 1100

2% Cu/Ce0 ₂ 300 390 390

8% Cu/Ce0 ₂ 300 560 560

a Reaction Temperature

b Time window for 100% NO conversion

c Time window for 100% N ₂ selectivity EXAMPLE 4

[0076] This example provides a description of the use of different catalysts.

[0077] Commercial Ce0 ₂ , 5% Cu/Al ₂ 03 and 5% Cu/Ce0 ₂ catalysts underwent the activation pretreatment described in Example 2. These catalysts were compared as catalysts for direct NO decomposition at 30 °C. All three catalysts achieved 100% NO conversion and 100 % N ₂ selectivity. But Ce0 ₂ , 5% Cu/Al ₂ 0 ₃ and 5% Cu/Ce0 ₂ catalysts showed different catalytic lifetimes, which were 30, 3,5 and 450 mins, respectively, indicating that synergistic effects between Cu and Ce0 ₂ not only had good capacity of NO decomposition, but also was able to retard the deactivation of Cu/Ce0 ₂ . Detailed results are shown in Figure 5.

EXAMPLE 5

[0078] This example provides a description of use of different catalysts

[0079] 5% Cu/Ce0 ₂ underwent pre-described activation pretreatment was used as catalyst for direction NO decomposition at 30 °C and 300 °C. At 30 °C, the catalyst achieved 100% NO conversion for 450 mins. 100 % N ₂ selectivity lasted for 450 mins. At 300 °C, the catalyst achieved 100% NO conversion for 1100 mins. 100 % N ₂ selectivity lasted for 1100 mins. The comparison indicated that relatively high temperature could prolong the lifetime of the catalyst. Detailed results are shown in Figure 6.

EXAMPLE 6

[0080] This example provides a description of use of different catalysts.

[0081] 2% Cu/Ce0 ₂ , 5% Cu/Ce0 ₂ , and 8% Cu/Ce0 ₂ catalysts underwent the activation pretreatment described in Example 2 and were used as catalyst for direct NO decomposition at 300 °C. The lifetime of these catalysts were 390, 1100, and 560 mins, respectively. These data indicate that 5% Cu loading was optimal for NO decomposition. Detailed results are shown in Figure 7.

EXAMPLE 7

[0082] This example provides a description of catalyst regeneration.

[0083] 5% Cu/Ce203 underwent the activation pretreatment described in Example 2 and was used as a catalyst for direct NO decomposition at 30 °C. After deactivation, the catalyst was regenerated by 5% ¾ and the catalytic activity recovered. The regenerated catalyst achieved 100% NO conversion for nearly 450 mins. 100 % N2 selectivity lasted for 450 mins. Detailed results are shown in Figure 8.

EXAMPLE 8

[0084] This example provides a description of the effect of oxygen on methods of present disclosure.

[0085] The effect of oxygen was investigated. Oxygen is a typical component in emissions of automobiles and power plants. 5% O2 was added into direct NO decomposition at 30 °C over 5% Cu/Ce203, which underwent the activation pretreatment described in Example 2. The addition of oxygen accelerated the deactivation of catalyst from 450 mins to 150 mins. However, the catalyst was regenerated by 5% H2 or CO. The activity and lifetime were recovered via regeneration. Detailed results are shown in Figure 9.

EXAMPLE 9

[0086] This example provides a description of industrial application of catalysts of the present disclosure.

[0087] The catalyst and methods can be used in an industrial design/system of application of a deNOx system. An example of such a design is shown Figure 4.

[0088] Figure 4 illustrates reaction conditions. Cu/Ce02 series catalyst of the present disclosure are synthesized and loaded into the packed bed of the reactor system. To activate the catalyst, hydrogen reduction is implemented followed by helium pretreatment which was described in Example 2. The reactor is adjusted to its optimum temperature depending on operating conditions. The NO inlet is opened after catalysts are activated and hydrogen or helium inlets are closed. After the catalyst is deactivated, the NO inlet can be closed and catalyst is reactivated with hydrogen. A parallel alignment of this reactor design can be implemented to ensure sufficient amount of activated catalysts are operational for continuous NOx decomposition.

EXAMPLE 10

[0089] This example provides a description of uses of nanoparticles of the present disclosure.

[0090] NOx can be decomposed using Cu/Ce02 at room temperature. Activation of

Cu/Ce02 requires H2 gas, presumably to produce oxygen vacancy. At room temperature, Cu/Ce02 exhibits 100% of NO to N ₂ . The reaction, however, yields less O2 than would be stoichiometrically predicted, presumably because of a redox reaction between Cu/Ce02 and NO. The conditions used were an activation cycle of 5% Irh/He at 500 °C at a rate of 50 mL/min for 2 h, followed by another activation cycle of He at room temperature at a rate of 50 mL/min for 3 h, followed by another activation He from room temperature to 500 °C at 50 mL/min for 2 h, and finally decomposition of NO via 500 ppm NO/He at room temperature at a rate of 20 mL/min. See Figure 13.

[0091] NO decomposition was determined using Ce02 and C11/AI2O3 as controls.

Ce02 or CU AI2O3 shows some NO conversion, but not than longer than 50 minutes. It is considered that activity of Cu Ce02 is not because of a redox reaction, but rather it is due to unique interfacial sites and/or synergistic effects. The conditions used were an activation cycle of 5% H2/He at 500 °C at a rate of 50 mL/min for 2 h, followed by another activation cycle of He at room temperature at a rate of 50 mL/min for 3 h, followed by another activation He from room temperature to 500 °C at 50 mL/min for 2 h, and finally

decomposition of NO via 500 ppm NO/He at room temperature at a rate of 20 mL/min. See Figure 14.

[0092] To determine if temperature affected the catalytic capacity of Cu Ce02, the catalyst was subjected to similar conditions as described above, but at 300 °C during NO treatment. The catalyst remained active for 1200 minutes at 300 °C. O2 stoichiometry was still lower than predicted; however, conversion of NO to N2 was still 100%. The degradation was not due to oxidation of the catalysts because oxidation should have occurred faster at 300 °C than at room temperature. The conditions used were an activation cycle of 5% H2/He at 500 °C at a rate of 50 mL/min for 2 h, followed by another activation cycle of He at room temperature at a rate of 50 mL/min for 3 h, followed by another activation He from room temperature to 500 °C at 50 mL/min for 2 h, and finally decomposition of NO via 500 ppm NO/He at room temperature or 300 °C at a rate of 20 mL/min. See Figure 15.

[0093] Further, it was determined that 5% copper loading achieved desirable results.

These data indicate there is no reduction of NO by Cu, one would expect higher loading would yield a longer lifetime. See Figure 16. The conditions used were an activation cycle of 5% H2/He at 500 °C at a rate of 50 mL/min for 2 h, followed by another activation cycle of He at room temperature at a rate of 50 mL/min for 3 h, followed by another activation He from room temperature to 500 °C at 50 mL/min for 2 h, and finally decomposition of NO via 500 ppm NO/He at room temperature at a rate of 20 mL/min.

[0094] It was determined that the catalyst could be regenerated by H2 treatment.

Presumably this restores oxygen vacancy. It is expected that lower temperature (e.g., 300 °C) would work for regeneration. See Figure 17. The conditions used were an activation cycle of 5% H2/He at 500 °C at a rate of 50 mL/min for 2 h, followed by another activation cycle of He at room temperature at a rate of 50 mL/min for 3 h, followed by another activation He from room temperature to 500 °C at 50 mL/min for 2 h, decomposition of NO via 500 ppm NO/He at room temperature at a rate of 20 mL/min, a regeneration cycle of 5% H2/He, at 500 °C at a rate of 50 mL/min for 1 hour. Following regeneration, the catalyst was used for NO decomposition using 500 ppm NO at room temperature at a rate of 20 mL/min.

[0095] Cu Ce02 can selectively decompose NO in the presence of extra O2. This reduces the lifetime of the catalyst; however, it can be regenerated by using H2 or CO. See

Figure 18. The conditions used were an activation cycle of 5% H2/He at 500 °C at a rate of 50 mL/min for 2 h, followed by another activation cycle of He at room temperature at a rate of 50 mL/min for 3 h, followed by another activation He from room temperature to 500 °C at 50 mL/min for 2 h, decomposition of NO via 500 ppm NO and 5% O2 at room temperature at a rate of 20 mL/min. Conditions for regeneration include 5% H2/He at 500 °C at a rate of 50 mL/min for 1 h or % CO/He at 500 °C at a rate of 50 mL/min for 1 h. After either cycle of regeneration, NO decomposition activity was 100% recovered.

[0096] It is considered that the catalytic mechanism of Cu Ce02 is based on interplay between Cu surface and oxygen vacancy at the Cu/Ce02 interface generates active sites for NO decomposition. A shorter distance between neighboring oxygen vacancies provides stronger compression between NOad than Cu-ZSM-5. Further, degradation caused by the undesired side reaction: produced O2 fill in the oxygen vacancy. See Figure 19. [0097] Figure 20 shows examples of catalyst morphology (e.g., nanoparticles and nanorods) and composition (e.g., doped CeC nanoparticle compositions and copper species alloys).

[0098] Figure 21 shows use of catalysts in NSR-type operations. This would include reactivation of the catalyst using alternative lean-rich combustion conditions, storing C , making it active at room temperature, and increasing the lifetime. Further, SCR using Fh,

[0099] Although the present disclosure has been described with respect to one or more particular embodiments and/or examples, it will be understood that other embodiments and/or examples of the present disclosure may be made without departing from the scope of the present disclosure.