CN114984967B - Cobalt oxide catalyst, method for preparing the same, and method for decomposing ammonia - Google Patents
Cobalt oxide catalyst, method for preparing the same, and method for decomposing ammonia Download PDFInfo
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- CN114984967B CN114984967B CN202210732503.2A CN202210732503A CN114984967B CN 114984967 B CN114984967 B CN 114984967B CN 202210732503 A CN202210732503 A CN 202210732503A CN 114984967 B CN114984967 B CN 114984967B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/082—Decomposition and pyrolysis
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
The invention provides a cobalt oxide catalyst, a preparation method thereof and a method for decomposing ammonia, wherein the preparation method of the cobalt oxide catalyst comprises the following steps: dissolving an alkaline reagent containing Na ions or K ions in water to obtain a precipitant solution; dissolving cobalt precursor in water to obtain a precursor solution; dropwise adding the precipitant solution into the precursor solution until the pH reaches a certain value, and performing aging, suction filtration, washing and drying treatment to obtain a crude catalyst; roasting the crude catalyst to obtain a cobalt oxide catalyst; wherein the cobalt oxide catalyst comprises Na or K doped cobalt oxide. The Na or K doped cobalt oxide can economically decompose NH 3 The cobalt oxide catalyst prepared by the method has higher activity, does not load on a carrier or is compounded with other metal elements, and has low cost, and obviously has higher ammonia decomposition activity.
Description
Technical Field
The invention relates to the field of environmental catalysis, in particular to a cobalt oxide catalyst, a preparation method thereof and a method for decomposing ammonia.
Background
Ammonia has a high energy density and octane number and is also a carrier of hydrogen energy. When being independently used as fuel, the fuel has high energy required for ignition, low flame propagation speed and NO in tail gas x High emissions, and the like, often require the introduction of additives. One of the solutions is to use the product H of the catalytic decomposition of ammonia 2 Can improve the combustion performance of ammonia and reduce the NO in tail gas x Is arranged in the air. It follows that the key reaction of ammonia decomposition is involved, whether directly as fuel or for purifying hydrogen. In recent years, continuous research cases prove that the ammonia decomposition hydrogen production has certain economic feasibility. Because of the high activation energy required for the ammonolysis reaction, the temperature required for the reaction needs to be reduced by adopting a proper catalyst to reduce energy consumption, and meanwhile, the cost and economic benefit of catalyst preparation need to be considered.
Disclosure of Invention
Based on the above, the invention provides a preparation method of cobalt oxide catalyst and a method for decomposing ammonia, which can economically decompose NH by adopting Na or K doped cobalt oxide 3 The catalyst has higher activity, is not loaded on a carrier or is compounded with other metal elements, and has low cost.
According to one aspect of the present invention, there is provided a method for preparing a cobalt oxide catalyst, comprising:
dissolving an alkaline reagent containing Na ions or K ions in water to obtain a precipitant solution;
dissolving cobalt precursor in water to obtain a precursor solution;
dropwise adding the precipitant solution into the precursor solution until the pH reaches a certain value, and performing aging, suction filtration, washing and drying treatment to obtain a crude catalyst;
roasting the crude catalyst in a muffle furnace to obtain the cobalt oxide catalyst;
wherein the cobalt oxide catalyst comprises Na or K doped cobalt oxide, preferably Co (NO 3 ) 2 ·6H 2 O、CoSO 4 ·7H 2 O or CoCl 2 ·6H 2 O；
The alkaline reagent is preferably NaOH or K 2 CO 3 Or KOH.
According to an embodiment of the present invention, the cobalt precursor is a hydrate of a divalent cobalt salt.
According to an embodiment of the present invention, the pH value ranges from 9.0 to 10.0.
According to the embodiment of the invention, the roasting temperature is 550-600 ℃, the roasting time is 3-4h, and the heating rate is 5-10 ℃/min.
According to an embodiment of the invention, the aging time is 3-5 hours.
According to another aspect of the present invention, there is provided a cobalt oxide catalyst prepared by the above preparation method, wherein the cobalt oxide catalyst comprises Na or K doped cobalt oxide.
According to another aspect of the present invention, there is provided a method for using the above cobalt oxide catalyst for ammonia decomposition, comprising:
at NH 3 Activating the cobalt oxide catalyst by heating under Ar atmosphere to reduce the cobalt oxide catalyst to metallic Co and NH 3 Decomposition into H at the active site of the above metallic Co 2 And N 2 And desorbing;
wherein the cobalt oxide catalyst comprises Na or K doped cobalt oxide.
According to an embodiment of the present invention, wherein the NH is 3 NH in Ar atmosphere 3 Accounting for 5 to 100 percent of the total volume.
According to an embodiment of the present invention, in the case where the cobalt oxide catalyst is reduced to Co in a metallic state, the Na or K is in a highly dispersed state.
According to an embodiment of the present invention, the Na or K has an electronic interaction with the metallic Co, so as to inhibit sintering and agglomeration of the active sites of the metallic Co.
According to the embodiment of the invention, the activation temperature of the cobalt oxide catalyst is 480-520 ℃.
From the above technical scheme, the cobalt oxide catalyst for ammonia decomposition provided by the invention has the following beneficial effects:
the Na or K doped cobalt oxide can economically decompose NH 3 The catalyst has higher activity, is not loaded on a carrier or is compounded with other metal elements, and has low cost. Compared with the existing catalyst for ammonia decomposition (ammonia decomposition conversion rate below 600 ℃ is lower than 50%), the cobalt oxide catalyst prepared by the method has obviously higher ammonia decomposition activity (the ammonia decomposition conversion rate at 500 ℃ can reach almost 100%). Under the same test conditions, the activity of the cobalt oxide catalyst prepared by the method is higher than that of cobalt oxide catalysts prepared by other methods. The preparation process is simple, the cost is low, and the industrial production can be realized.
Drawings
FIG. 1 is a graph comparing ammonia conversion for a cobalt oxide catalyst of an embodiment of the invention with a pure cobalt oxide catalyst;
FIG. 2 is a graph comparing ammonia conversion for a sample of cobalt oxide catalyst in an example of the invention;
FIG. 3 is a chart of XRD diffraction patterns of a sample of cobalt oxide catalyst prior to catalysis in accordance with an embodiment of the present invention;
fig. 4 is an XRD diffractogram after catalysis of a cobalt oxide catalyst sample in an embodiment of the invention.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
In the related art, noble metal catalysts represented by Ru groups have high ammonia decomposition activity, but are difficult to put into large-scale application due to high price. The transition metal catalyst is relatively environment-friendly, is cheap and easy to obtain, and is one of catalyst systems hopeful to replace noble metals.
Among the transition metal catalysts, an ammonia decomposition catalyst containing cobalt as a main active component has been attracting attention in recent years because of its high ammonia decomposition activity. At present, pure cobalt oxide is used as a catalyst, and due to the reasons of small specific surface area, easy sintering at high temperature and the like of the pure cobalt oxide, ammonia decomposition activity is low, and the pure cobalt oxide is often required to be loaded on a carrier or compounded with other metal elements, so that the cost is increased in a complex preparation process, and the industrial application is not facilitated.
According to an aspect of the present general inventive concept, there is provided a method of preparing a cobalt oxide catalyst, comprising:
step one: dissolving an alkaline reagent containing Na ions or K ions in water to obtain a precipitant solution;
step two: dissolving cobalt precursor in water to obtain a precursor solution;
step three: dropwise adding the precipitant solution into the precursor solution until the pH reaches a certain value, and performing aging, suction filtration, washing and drying treatment to obtain a crude catalyst;
step four: roasting the crude catalyst to obtain a cobalt oxide catalyst;
wherein the cobalt oxide catalyst comprises Na or K doped cobalt oxide.
The Na or K doped cobalt oxide can economically decompose NH 3 The catalyst has higher activity, is not loaded on a carrier or is compounded with other metal elements, and has low cost. Compared with the existing pure cobalt oxide catalyst for ammonia decomposition (ammonia decomposition conversion rate below 600 ℃ is lower than 50%), the cobalt oxide catalyst prepared by the invention obviously has higher ammonia decomposition activity (the ammonia decomposition conversion rate at 500 ℃ can reach almost 100%). Under the same test conditions, the activity of the cobalt oxide catalyst prepared by the method is higher than that of cobalt oxide catalysts prepared by other methods. The preparation process is simple, the cost is low, and the industrial production can be realized.
According to an embodiment of the present invention, in the first step, the alkaline reagent containing Na ion or K ion may be NaOH or K 2 CO 3 Or KOH.
In step one, according to embodiments of the present invention, the precipitant (NaOH, KOH, etc.) simultaneously acts as an ammonia decomposing co-agent. The Na/K content in the cobalt oxide can be effectively regulated by changing the adding amount of the precipitant, the times of suction filtration and washing and the like.
According to an embodiment of the invention, in step one, the water is high purity water.
According to an embodiment of the invention, in step two, the cobalt precursor is a hydrate of a divalent cobalt salt.
In step two, according to an embodiment of the present invention, the cobalt precursor may be Co (NO 3 ) 2 ·6H 2 O、CoSO 4 ·7H 2 O or CoCl 2 ·6H 2 Hydrates of other divalent cobalt salts such as O.
According to an embodiment of the invention, in step three, the pH value is in the range of 9.0-10.0. For example, in the third step, the pH may be 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0 or may be selected according to the actual situation.
According to an embodiment of the invention, in the third step, the aging time is 3-5 hours.
According to embodiments of the present invention, for example, in the third step, the aging time may be 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or may be selected according to practical situations.
According to the embodiment of the invention, in the fourth step, the roasting temperature is 550-600 ℃, the roasting time is 3-4h, and the heating rate is 5-10 ℃/min.
According to an embodiment of the present invention, for example, in the fourth step, the temperature of the firing may be 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃.
According to embodiments of the present invention, for example, in step four, the firing time may be 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h, 4h.
According to an embodiment of the present invention, for example, in step four, the heating rate may be 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min.
According to another aspect of the present invention, there is provided a cobalt oxide catalyst prepared by the preparation method, wherein the cobalt oxide catalyst comprises Na or K doped cobalt oxide.
According to another aspect of the present invention there is provided a process for using the cobalt oxide catalyst for ammonia decomposition comprising:
at NH 3 Under Ar atmosphere, heating and activating the cobalt oxide catalyst, reducing the cobalt oxide catalyst to metallic Co, and leading NH to be obtained 3 Decomposition to H at the active site of Co in metallic form 2 And N 2 And desorbing;
wherein the cobalt oxide catalyst comprises Na or K doped cobalt oxide.
According to an embodiment of the invention, the method for ammonia decomposition is specifically: first at 15% NH 3 Activating the catalyst at high temperature under Ar atmosphere, and adding Co into the catalyst 3 O 4 Co reduced to the metallic state acts as the primary active site in the ammonolysis reaction. NH (NH) 3 Decomposition to H at the active site 2 And N 2 And desorbed.
For unsupported catalysts, livingSintering and agglomeration of sex sites are important factors affecting ammonia decomposition activity. On the one hand, the electronic interaction between the alkali metals Na and K and Co can effectively inhibit the sintering and agglomeration of the active sites; on the other hand, the alkali metals Na and K can increase the alkalinity of the catalyst surface and promote the ammonia decomposition product N 2 Thereby increasing ammonia decomposition activity.
According to an embodiment of the invention, wherein NH 3 NH in Ar atmosphere 3 Accounting for 5 to 100 percent of the total volume.
According to an embodiment of the invention, wherein NH 3 NH in Ar atmosphere 3 May comprise 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% of the total volume.
According to an embodiment of the invention, wherein, preferably, NH 3 NH in Ar atmosphere 3 Accounting for 12 to 17 percent of the total volume.
According to an embodiment of the invention, wherein NH 3 NH in Ar atmosphere 3 Can account for 12%, 13%, 14%, 15%, 16%, 17% of the total volume.
According to an embodiment of the invention, wherein Na or K is in a highly dispersed state in the case of reduction of the cobalt oxide catalyst to Co in a metallic state.
According to an embodiment of the invention, wherein the activation temperature of the cobalt oxide catalyst is 480-520 ℃.
According to an embodiment of the present invention, wherein the activation temperature of the cobalt oxide catalyst may be 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃.
The following detailed description of the present invention is given by way of example only, and not by way of limitation.
Example 1: preparation of the samples.
Preparation of sample 1:
step one: dissolving 8g of NaOH in 200mL of high-purity water to obtain a precipitant solution;
step two: 5.821g Co (NO) 3 ) 2 ·6H 2 O is dissolved in 100mL of high-purity water to obtain a precursorA solution;
step three: dropwise adding the precipitant solution into the precursor solution until the pH value is=9, continuously stirring for 1h, stopping stirring, and aging for 3h; filtering and washing, and drying the obtained solid to obtain a crude catalyst;
step four: the crude catalyst was put into a muffle furnace at 600℃for 4 hours with a heating rate of 10℃per minute to obtain a cobalt oxide catalyst as sample 1.
Preparation of sample 2:
step one: will be 27.64g K 2 CO is dissolved in 180mL of high-purity water to obtain a precipitant solution;
step two: 5.622g CoSO 4 ·7H 2 O is dissolved in 90mL of high-purity water to obtain a precursor solution;
step three: dropwise adding the precipitant solution into the precursor solution until the pH=9.5, continuously stirring for 2 hours, stopping stirring, and aging for 4 hours; filtering and washing, and drying the obtained solid to obtain a crude catalyst;
step four: roasting the mixture for 3 hours at 600 ℃ in a muffle furnace, and heating at a rate of 5 ℃/min to obtain a cobalt oxide catalyst, wherein the cobalt oxide catalyst is taken as a sample 2.
Preparation of sample 3:
step one: 11.22g KOH was dissolved in 220mL high purity water to give a precipitant solution;
step two: 4.759g CoCl 2 ·6H 2 O is dissolved in 110mL of high-purity water to obtain a precursor solution;
step three: dropwise adding the precipitant solution into the precursor solution until the pH=10, continuously stirring for 1.5 hours, stopping stirring, and aging for 5 hours; filtering and washing, and drying the obtained solid to obtain a crude catalyst;
step four: roasting the mixture for 3.5 hours at 550 ℃ in a muffle furnace, and obtaining a cobalt oxide catalyst as a sample 3 at a heating rate of 10 ℃/min.
Preparation of comparative samples:
step one: 5.820g of Co (NO 3) 2.6H2O and 5.044g of citric acid are dissolved in 20mL of high-purity water, and the mixture is stirred until the mixture is completely evaporated to dryness, so as to obtain a crude product;
step two: the crude product was transferred to an oven at 105 ℃ overnight, followed by grinding, and roasting in a muffle furnace at 600 ℃ for 3 hours at a heating rate of 5 ℃/min to obtain a pure cobalt oxide catalyst as a comparative sample.
Example 2: the ammonia conversion of the samples was investigated.
FIG. 1 is a graph comparing ammonia conversion for a cobalt oxide catalyst of an embodiment of the invention with a pure cobalt oxide catalyst;
at NH 3 Heating the catalyst provided by the sample 1 and the comparative sample in an Ar atmosphere;
wherein the catalysis conditions are as follows: [ NH ] 3 ]15% Ar is balance gas, total flow 50mL/min, GHSV=25,000 mL g cat -1 h -1 ，500℃，1h：
As can be seen from FIG. 1, compared with the existing catalyst for ammonia decomposition, the ammonia decomposition conversion rate of the comparative sample below 600 ℃ is lower than 50%, the cobalt oxide catalyst prepared by the invention obviously has higher ammonia decomposition activity, and the ammonia decomposition conversion rate of the sample 1 at 500 ℃ can reach almost 100%. Under the same test conditions, the activity of the cobalt oxide catalyst prepared by the method is higher than that of cobalt oxide catalysts prepared by other methods. The preparation process is simple, the cost is low, and the industrial production can be realized.
FIG. 2 is a graph comparing ammonia conversion for a sample of cobalt oxide catalyst in an example of the invention.
At NH 3 Under Ar atmosphere, the cobalt oxide catalysts provided by the sample 1, the sample 2 and the sample 3 are heated and activated, and the cobalt oxide catalysts provided by the sample 1, the sample 2 and the sample 3 are reduced to metallic Co to enable NH 3 Decomposition to H at the active site of Co in metallic form 2 And N 2 And desorbing;
wherein the catalysis conditions are as follows: [ NH ] 3 ]15% Ar is balance gas, total flow 50mL/min, GHSV=25,000 mL g cat -1 h -1 ，500℃，1h：
As can be seen in fig. 2, all three samples had better conversions, with initial conversion of sample 1 being the highest, but near 600 degrees, the conversion of ammonia by the cobalt oxide catalyst provided by samples 1, 2 and 3 was almost 100%;
example 3: investigation of the catalyst Structure of the sample before and after catalysis
Fig. 3 is an XRD diffractogram before catalysis of a cobalt oxide catalyst sample in an embodiment of the invention.
Fig. 4 is an XRD diffractogram after catalysis of a cobalt oxide catalyst sample in an embodiment of the invention.
As can be seen from the XRD diffraction patterns, the fresh samples not participating in the catalytic reaction provided by sample 1, sample 2 and sample 3 all appear to be attributed to Co 3 O 4 Is a diffraction peak of (2).
As can be seen from the XRD diffractograms, samples 1, 2 and 3 provided the catalytically reacted samples showed diffraction peaks ascribed to metallic Co, as shown in fig. 4.
As can be seen from the XRD diffractograms, no Na/K-related diffraction peaks were observed for all of the fresh samples and reacted samples provided by samples 1, 2 and 3, indicating Na/K in a highly dispersed state.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (5)
1. A method of using a cobalt oxide catalyst for ammonia decomposition, comprising:
at NH 3 Activating cobalt oxide catalyst by heating under Ar atmosphere to reduce the cobalt oxide catalyst to metallic Co and NH 3 Decomposition to H at the active site of the metallic Co 2 And N 2 And desorbing;
wherein the cobalt oxide catalyst comprises Na or K doped cobalt oxide;
the NH is 3 NH in Ar atmosphere 3 Accounting for 5-100% of the total volume;
in the case where the cobalt oxide catalyst is reduced to Co in a metallic state, the Na or K is in a highly dispersed state;
the activation temperature of the cobalt oxide catalyst is 480-520 ℃;
the preparation method of the cobalt oxide catalyst comprises the following steps:
dissolving an alkaline reagent containing Na ions or K ions in water to obtain a precipitant solution;
dissolving cobalt precursor in water to obtain a precursor solution;
dropwise adding the precipitant solution into the precursor solution until the pH reaches a certain value, and performing aging, suction filtration, washing and drying treatment to obtain a crude catalyst;
roasting the crude catalyst to obtain the cobalt oxide catalyst;
wherein the cobalt oxide catalyst comprises Na or K doped cobalt oxide.
2. A method according to claim 1, wherein the cobalt precursor is a hydrate of a divalent cobalt salt, preferably Co (NO 3 ) 2 ·6H 2 O、CoSO 4 ·7H 2 O or CoCl 2 ·6H 2 O；
The alkaline reagent is preferably NaOH or K 2 CO 3 Or KOH.
3. The method of claim 1, wherein the pH is in the range of 9.0-10.0.
4. The method of claim 1, wherein the firing temperature is 550-600 ℃, the firing time is 3-4 hours, and the temperature rise rate is 5-10 ℃/min.
5. The method of claim 1, wherein the aging time is 3-5 hours.
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| JP2011224554A (en) * | 2010-03-31 | 2011-11-10 | Nippon Shokubai Co Ltd | Catalyst for decomposing ammonia, method for producing the catalyst, and method for producing hydrogen using the catalyst |
| CN113198476A (en) * | 2021-04-09 | 2021-08-03 | 东南大学 | Transition metal doped ammonia decomposition catalyst and preparation method and application thereof |
| CN113996305A (en) * | 2021-11-23 | 2022-02-01 | 辽宁大学 | Medium-low temperature catalytic decomposition of N2O composite oxide catalyst and preparation method and application thereof |
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| WO2009142520A1 (en) * | 2008-05-21 | 2009-11-26 | Uniwersytet Jagiellonski | Catalyst for low-temperature decomposition of dinitrogen oxide and a process for the preparation thereof |
| US8962518B2 (en) * | 2009-03-17 | 2015-02-24 | Nippon Shokubai Co., Ltd. | Catalyst for production of hydrogen and process for producing hydrogen using the catalyst, and catalyst for combustion of ammonia, process for producing the catalyst and process for combusting ammonia using the catalyst |
| CN103771542B (en) * | 2014-01-22 | 2015-02-18 | 广东工业大学 | Preparation method for high-heat stability cobalt oxide with large specific surface |
| US11478784B2 (en) * | 2020-02-04 | 2022-10-25 | Saudi Arabian Oil Company | Catalyst compositions for ammonia decomposition |
| CN111939907A (en) * | 2020-09-21 | 2020-11-17 | 浙江工业大学 | Catalyst for low-temperature ammonia decomposition hydrogen production and preparation method and application thereof |
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| JP2011224554A (en) * | 2010-03-31 | 2011-11-10 | Nippon Shokubai Co Ltd | Catalyst for decomposing ammonia, method for producing the catalyst, and method for producing hydrogen using the catalyst |
| CN113198476A (en) * | 2021-04-09 | 2021-08-03 | 东南大学 | Transition metal doped ammonia decomposition catalyst and preparation method and application thereof |
| CN113996305A (en) * | 2021-11-23 | 2022-02-01 | 辽宁大学 | Medium-low temperature catalytic decomposition of N2O composite oxide catalyst and preparation method and application thereof |
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