CN115672349A - Metal oxide catalyst with hollow nanotube structure and preparation method and application thereof - Google Patents
Metal oxide catalyst with hollow nanotube structure and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 239000002071 nanotube Substances 0.000 title claims abstract description 78
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- 238000002360 preparation method Methods 0.000 title abstract description 23
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- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
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- MCIGQJNJTFILQA-UHFFFAOYSA-N [K].[Co].[Mn] Chemical compound [K].[Co].[Mn] MCIGQJNJTFILQA-UHFFFAOYSA-N 0.000 claims abstract description 4
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims abstract description 4
- MIAJZAAHRXPODB-UHFFFAOYSA-N cobalt potassium Chemical compound [K].[Co] MIAJZAAHRXPODB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
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- 239000002243 precursor Substances 0.000 claims description 61
- 238000001354 calcination Methods 0.000 claims description 40
- 239000004071 soot Substances 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 10
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 8
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- 239000007789 gas Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
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- -1 polyethylene pyrrolidone Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
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- 238000002485 combustion reaction Methods 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 4
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
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- 235000011056 potassium acetate Nutrition 0.000 description 3
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 230000006978 adaptation Effects 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention discloses a hollow nanotube structure metal oxide catalyst, which is a nanotube structure single metal oxide catalyst and is prepared from a single metal: manganese, iron, cobalt, nickel, copper, lanthanum, cerium and oxygen, expressed as: mnO (MnO) x 、FeO x 、CoO x 、NiO x 、CuO x 、LaO x 、CeO x (ii) a Or the catalyst is a composite metal oxide catalyst with a nanotube structure, and is prepared from a composite metal: potassium manganese, potassium cobalt, manganese cobalt, potassium manganese cobalt and oxygen. The preparation method provided by the invention can be applied to the preparation of a plurality of single metal and composite metal oxide catalysts, and has the advantages of simple preparation process and practicabilityStrong, high efficiency, low cost and easy realization of large-scale production.
Description
Technical Field
The invention relates to the technical field of catalyst material preparation, in particular to a metal oxide catalyst with a hollow nanotube structure and a preparation method and application thereof.
Background
Diesel engines are widely used in the fields of automobiles, ships, light trucks, heavy machinery, etc., with excellent thermal efficiency and durability. However, diesel engines are also considered to be one of the main sources of soot particulate emissions, an important cause of haze weather. With the increase of environmental awareness, the emission standard of the diesel engine is more and more strict. Therefore, it is imperative to eliminate soot particles to meet emission standards. At present, post-treatment techniques are considered to be one of the effective methods for removing soot particles. However, since the spontaneous combustion temperature (550-650 ℃) of soot particles is higher than the exhaust temperature (150-450 ℃) of a diesel engine, the development of a novel catalyst with low cost and excellent catalytic performance is one of the main challenges in the application of aftertreatment technology, and the development of the research on catalytic combustion of soot particles has important environmental protection significance.
The catalytic combustion of soot particles is used as a special heterogeneous catalytic reaction, and because of the characteristics of three-phase catalysis of gas (reaction gas) -solid (soot particles) -solid (catalyst), the morphology and structure of the catalyst have a decisive role in the performance of the catalyst, so that how to synthesize the catalyst with special morphology and specific structure by using a simple and easy preparation method is always the direction of common efforts of researchers.
Disclosure of Invention
In view of the above, the present invention discloses a metal oxide catalyst with a hollow nanotube structure, and a preparation method and an application thereof;
in a first aspect, the present invention provides a metal oxide catalyst with a hollow nanotube structure, wherein the catalyst is a single metal oxide catalyst with a nanotube structure, and the metal oxide catalyst is prepared from a single metal: manganese, iron, cobalt, nickel, copper, lanthanum, cerium and oxygen, expressed as: mnO x 、FeO x 、CoO x 、NiO x 、CuO x 、LaO x 、CeO x (ii) a Or the catalyst is a composite metal oxide catalyst with a nanotube structure, and is prepared from a composite metal: potassium manganese, potassium cobalt, manganese cobalt, potassium manganese cobalt and oxygen.
Further, the catalyst is a nanotube structure composite metal oxide catalyst: k 0.5 MnO x 、K 0.5 CoO x 、MnCoO x 、K 0.5 MnCoO x 。
In a second aspect, the present invention also provides a method of preparing a catalyst comprising: the metal oxide catalyst is prepared by using metal nitrate, metal acetate, glacial acetic acid and polyethylene pyrrolidone as raw materials through dissolution, centrifugal spinning, drying and roasting.
Further, polyvinylpyrrolidone has an average molecular weight of 1300000 and a polymerization degree of K =88-96.
Further, the preparation method specifically comprises the following steps: weighing a certain amount of metal nitrate and metal acetate according to a stoichiometric ratio, dissolving the metal nitrate and the metal acetate in ethanol and water, adding a glacial acetic acid solution, adding polyvinylpyrrolidone after uniformly stirring, stirring for 20min under a water bath condition at 25-70 ℃ to obtain a homogeneous transparent sol precursor, and collecting the precursor by using a medical injector;
slowly injecting the collected precursor solution into a centrifuge of a centrifugal spinning device, and collecting the precursor solution at a position 13.5cm away from the centrifuge at the rotating speed of 1000-4000rpm to obtain precursor fibers;
and drying the collected fibers in an oven at 80 ℃ for 24 hours, and calcining the dried fibers in a muffle furnace to obtain the metal oxide catalyst.
Furthermore, the temperature is raised to 300 ℃ by adopting a muffle furnace at the temperature raising rate of 2 ℃/min, the temperature is raised to 550 ℃ within 20min after the temperature is maintained for 1h, and the calcination is carried out for 6h at 550 ℃.
In a third aspect, the invention further provides an application of the metal oxide catalyst with the hollow nanotube structure, and the catalyst is applied to catalytic combustion reaction of soot particles in diesel engine exhaust.
The preparation method can be applied to the preparation of various single metal and composite metal oxide catalysts, and has the advantages of simple preparation process, strong practicability, high efficiency, low cost and easiness in realizing large-scale production.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or prior art solutions of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an XRD pattern of a hollow nanotube structured single metal oxide catalyst prepared in examples 1-7 of the present disclosure;
FIG. 2 is an XRD pattern of the composite metal oxide catalyst with hollow nanotube structure prepared in examples 8-11 of the present disclosure;
FIG. 3 is a scanning electron micrograph of a hollow nanotube structured single metal oxide catalyst prepared according to examples 1 to 7 of the disclosure;
FIG. 4 is a scanning electron micrograph of the hollow nanotube structured composite metal oxide catalyst prepared in examples 8 to 11 of the present disclosure.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of systems consistent with certain aspects of the invention, as detailed in the appended claims.
The hollow nanotube catalyst has extremely high reaction specific surface area due to the nanofiber structure, and the large aperture can enable soot particles to enter the inside of the nanotube and be influenced by high-speed reaction air flows from different directions in the nanotube to form Brownian-like motion, so that the soot particles continuously collide with the wall of the catalyst tube for many times, and the contact efficiency with the soot catalyst is remarkably improved.
In a first aspect, the present embodiment provides a metal oxide catalyst with a hollow nanotube structure, wherein the catalyst is a single metal oxide catalyst with a nanotube structure, and the metal oxide catalyst is prepared from a single metal: manganese, iron, cobalt, nickel, copper, lanthanum, cerium and oxygen, expressed as: mnO x 、FeO x 、CoO x 、NiO x 、CuO x 、LaO x 、CeO x (ii) a Or the catalyst is a composite metal oxide catalyst with a nanotube structure, and is prepared from composite metal: potassium manganese, potassium cobalt, manganese cobalt, potassium manganese cobalt and oxygen.
The catalyst is a composite metal oxide catalyst with a nanotube structure: k 0.5 MnO x 、K 0.5 CoO x 、MnCoO x 、K 0.5 MnCoO x 。K 0.5 MnO x K of (2): molar ratio of Mn 0.5 0.5 CoO x K of (2): molar ratio of Co is 0.5 x Mn of (2): molar ratio of Co 1, K 0.5 MnCoO x The molar ratio of Mn to Co of (1) is 0.5.
In a second aspect, the present invention provides a simple method for preparing a metal oxide catalyst material with a hollow nanotube structure. The method comprises the steps of taking metal nitrate and metal acetate as metal precursors, increasing the viscosity of the precursors by polyvinylpyrrolidone, preparing a metal oxide catalyst with a hollow nanotube structure by a centrifugal spinning method, and using the metal oxide catalyst as a catalyst to catalyze and combust soot particles in the tail gas of a diesel engine; the method comprises the following specific steps:
weighing a certain amount of metal nitrate and metal acetate according to a stoichiometric ratio, dissolving the metal nitrate and the metal acetate in a certain amount of ethanol and water, adding a small amount of glacial acetic acid solution, adding polyvinylpyrrolidone after uniformly stirring, stirring for 20min under a water bath condition (55 ℃) to obtain a homogeneous transparent sol precursor, and collecting the precursor by using a medical register. And slowly injecting the collected precursor solution into a centrifuge of a centrifugal spinning device, and collecting the precursor solution at a position 13.5cm away from the centrifuge at the rotating speed of 4000rpm to obtain precursor fibers. Drying the collected fibers in an oven at 80 ℃ for 24 hours, calcining the dried fibers in a muffle furnace, raising the temperature to 300 ℃ at a heating rate of 2 ℃/min, maintaining the temperature for 1 hour, raising the temperature to 550 ℃ within 20min, and calcining the fibers at 550 ℃ for 6 hours. Obtaining the hollow nanotube metal oxide catalyst.
In a third aspect, the present embodiment provides an application of the metal oxide catalyst material with a hollow nanotube structure, which is applied to a catalytic combustion reaction of soot particles in diesel engine exhaust, and the catalyst has high catalytic activity and stability, wherein the soot particles can be completely combusted and eliminated at a temperature below 361 ℃.
The centrifugal spinning method is rarely applied to the preparation of the shape of the hollow nanotube metal oxide catalyst and the application of soot catalytic combustion, the embodiment selects and utilizes low-cost metal nitrate and metal acetate as metal precursors, polyvinylpyrrolidone is used for increasing the viscosity of the precursors, and the nanotube metal oxide catalyst is obtained through dissolution, centrifugal spinning, drying and roasting.
Example 1
Preparation of MnO x Nanotube structured catalyst
Dissolving 4.902g of manganese acetate tetrahydrate in 7.5mL of mixed solution of ethanol, 2mL of water and 0.5mL of glacial acetic acid in a certain stoichiometric ratio, adding 1.9g of polyvinylpyrrolidone (Kw = 1300000), and magnetically stirring at 55 ℃ for 20min to obtain the manganese acetate tetrahydrateThe homogeneous sol precursor is collected by a medical register. Taking a commercial cotton candy machine, regulating the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotor at a constant speed, ejecting precursor fibers from small holes in the side surface of the rotor under the action of centrifugal force, and collecting the precursor fibers at a position 13.5cm away from the rotor by using a collecting rod. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in an air atmosphere, raising the temperature from room temperature to 300 ℃ at a speed of 2 ℃/min, calcining the fibers for 1h, raising the temperature to 550 ℃ within 20min, calcining the fibers at 550 ℃ for 6h, and then reducing the temperature to room temperature to obtain MnO x A hollow nanotube catalyst.
MnO x The XRD pattern of the hollow nanotube catalyst is shown in FIG. 1, from which it can be seen that the catalyst has significant Mn 2 O 3 Characteristic diffraction peak of (1). The SEM photograph is shown in FIG. 3, and the catalyst has a hollow nanotube structure with a mean diameter of 2.58 μm. The activity of the catalyst for catalytic combustion of soot particles is shown in table 1.
Example 2
Preparation of FeO x Nanotube-structured catalyst
4.04g of ferric nitrate nonahydrate with a certain stoichiometric ratio is dissolved in a mixed solution of 6mL of ethanol and 4mL of water, 2g of polyvinylpyrrolidone (Kw = 1300000) is added, and the mixture is magnetically stirred for 20min under the hydrothermal condition of 55 ℃ to obtain a homogeneous sol precursor which is collected by a medical registry. Taking a commercial cotton candy machine, regulating the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotor at a constant speed, ejecting precursor fibers from small holes in the side surface of the rotor under the action of centrifugal force, and collecting the precursor fibers at a position 13.5cm away from the rotor by using a collecting rod. Drying the collected fibers at 80 ℃ for 24h, then calcining the fibers in a muffle furnace in an air atmosphere, raising the temperature from room temperature to 300 ℃ at a speed of 2 ℃/min, raising the temperature to 550 ℃ at a speed of 20min after calcining for 1h, and lowering the temperature to room temperature after calcining for 6h at 550 ℃ to obtain FeO x A hollow nanotube catalyst.
FeO x The XRD pattern of the hollow nanotube catalyst is shown in FIG. 1, from which it can be seen that the catalyst has significant Fe 2 O 3 Characteristic diffraction peak of (1). The SEM photograph is shown in FIG. 3, and the catalyst has a hollow nanotube structure with an average diameter of 3.84 μm. The activity of the catalyst for catalytic combustion of soot particles is shown in table 1.
Example 3
Preparation of CoO x Nanotube-structured catalyst
2.989g of cobalt acetate tetrahydrate with a certain stoichiometric ratio is dissolved in a mixed solution of 7.5mL of ethanol, 2mL of water and 0.5mL of glacial acetic acid, 2.1g of polyvinylpyrrolidone (Kw = 1300000) is added, and the mixture is magnetically stirred for 20min under the hydrothermal condition of 55 ℃ to obtain a homogeneous sol precursor which is collected by a medical register. And (3) taking a commercial cotton candy machine, regulating the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotor at a constant speed, ejecting precursor fibers from small holes in the side surface of the rotor under the action of centrifugal force, and collecting the precursor fibers at a position 13.5cm away from the rotor by using a collecting rod. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in an air atmosphere, raising the temperature from room temperature to 300 ℃ at a speed of 2 ℃/min, calcining the fibers for 1h, raising the temperature to 550 ℃ at 20min, calcining the fibers at 550 ℃ for 6h, and then reducing the temperature to room temperature to obtain CoO x A hollow nanotube catalyst.
CoO x The XRD pattern of the hollow nanotube catalyst is shown in FIG. 1, from which it can be seen that the catalyst has significant Co 3 O 4 Characteristic diffraction peaks of (2). The SEM photograph is shown in FIG. 3, and the catalyst has a hollow nanotube structure with an average diameter of 2.16 μm. The activity of the catalyst for catalytic combustion of soot particles is shown in table 1.
Example 4
Preparation of NiO x Nanotube structured catalyst
2.908g of nickel nitrate hexahydrate with a certain stoichiometric ratio is dissolved in a mixed solution of 6mL of ethanol and 4mL of water, 2g of polyvinylpyrrolidone (Kw = 1300000) is added, and the mixture is magnetically stirred for 20min under the hydrothermal condition of 55 ℃ to obtain a homogeneous sol precursor which is collected by a medical registry. Taking a commercial cotton candy machine, and adjusting the rotating speed to 4000rpm under the condition of room temperaturePrecursor sol in the medical injector is slowly pushed into the rotor at a constant speed, the precursor is subjected to centrifugal force to eject precursor fibers from small holes on the side surface of the rotor, and the precursor fibers are collected by a collecting rod at a position 13.5cm away from the rotor. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in an air atmosphere, raising the temperature from room temperature to 300 ℃ at a speed of 2 ℃/min, raising the temperature to 550 ℃ after calcining for 1h within 20min, calcining at 550 ℃ for 6h, and then lowering the temperature to room temperature to obtain NiO x A hollow nanotube catalyst.
NiO x The XRD pattern of the hollow nanotube catalyst is shown in figure 1, and the catalyst has a characteristic NiO diffraction peak which is obvious from the pattern. The SEM photograph is shown in FIG. 3, and the catalyst has a hollow nanotube structure with a mean diameter of 2.68 μm. The activity of the catalyst for catalytic combustion of soot particles is shown in table 1.
Example 5
Preparation of CuO x Nanotube-structured catalyst
2.416g of copper nitrate trihydrate with a certain stoichiometric ratio is dissolved in a mixed solution of 5mL of ethanol and 5mL of water, 2g of polyvinylpyrrolidone (Kw = 1300000) is added, and the mixture is magnetically stirred for 20min under the hydrothermal condition of 55 ℃ to obtain a homogeneous sol precursor which is collected by a medical register. Taking a commercial cotton candy machine, regulating the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotor at a constant speed, ejecting precursor fibers from small holes in the side surface of the rotor under the action of centrifugal force, and collecting the precursor fibers at a position 13.5cm away from the rotor by using a collecting rod. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in air atmosphere, raising the temperature from room temperature to 300 ℃ at a speed of 2 ℃/min, raising the temperature to 550 ℃ after calcining for 1h for 20min, calcining at 550 ℃ for 6h, and then lowering the temperature to room temperature to obtain CuO x A hollow nanotube catalyst.
CuO x The XRD pattern of the hollow nanotube catalyst is shown in figure 1, and the catalyst has obvious characteristic diffraction peak of CuO. The SEM photograph is shown in FIG. 3, and the catalyst has a hollow nanotube structure with an average diameter of 3.90 μm. The catalyst catalytically burns soot particlesThe activity is shown in Table 1.
Example 6
Preparation of LaO x Nanotube-structured catalyst
4.33g of lanthanum nitrate hexahydrate in a certain stoichiometric ratio is dissolved in a mixed solution of 8mL of water and 2mL of ethanol, 1.6g of polyvinylpyrrolidone (Kw = 1300000) is added, and the mixture is magnetically stirred for 20min under the hydrothermal condition of 55 ℃ to obtain a homogeneous sol precursor which is collected by a medical registry. And (3) taking a commercial cotton candy machine, regulating the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotor at a constant speed, ejecting precursor fibers from small holes in the side surface of the rotor under the action of centrifugal force, and collecting the precursor fibers at a position 13.5cm away from the rotor by using a collecting rod. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in an air atmosphere, raising the temperature from room temperature to 300 ℃ at a speed of 2 ℃/min, calcining the fibers for 1h, raising the temperature to 550 ℃ within 20min, calcining the fibers at 550 ℃ for 6h, and then reducing the temperature to room temperature to obtain LaO x A hollow nanotube catalyst.
LaO x The XRD pattern of the hollow nanotube catalyst is shown in figure 1, and the catalyst has obvious LaOx characteristic diffraction peak. The SEM photograph is shown in FIG. 3, the catalyst has a hollow nanotube structure, and a large number of pore structures exist on the surface of the tube wall, and the average tube diameter is 3.38 μm. The activity of the catalyst for catalytic combustion of soot particles is shown in table 1.
Example 7
Preparation of CeO x Nanotube structured catalyst
4.342g of cerous nitrate hexahydrate with a certain stoichiometric ratio is dissolved in a mixed solution of 2mL of ethanol and 8mL of water, 1.625g of polyvinylpyrrolidone (Kw = 1300000) is added, and the mixture is magnetically stirred for 20min under the hydrothermal condition of 55 ℃ to obtain a homogeneous sol precursor which is collected by a medical registry. Taking a commercial cotton candy machine, adjusting the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotor at a constant speed, ejecting precursor fibers from small holes on the side surface of the rotor under the action of centrifugal force, and using the precursor fibers at a distance of 13.5cm away from the rotorCollecting by a collecting rod. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in an air atmosphere, raising the temperature from room temperature to 300 ℃ at a speed of 2 ℃/min, calcining the fibers for 1h, raising the temperature to 550 ℃ within 20min, calcining the fibers at 550 ℃ for 6h, and then reducing the temperature to room temperature to obtain CeO x A hollow nanotube catalyst.
CeO x The XRD pattern of the hollow nanotube catalyst is shown in FIG. 1, and it can be seen that the catalyst has obvious CeO 2 Characteristic diffraction peak of (1). The SEM photograph is shown in FIG. 3, the catalyst has a hollow nanotube structure, and a large number of pore structures exist on the surface of the tube wall, and the average tube diameter is 5.74 μm. The activity of the catalyst for catalytic combustion of soot particles is shown in table 1.
TABLE 1 Performance of catalytic Combustion of soot particles with a single metal oxide catalyst having a nanotube structure
Example 8
Preparation K 0.5 MnO x Nanotube structured catalyst
0.491g of potassium acetate and 4.902g of manganese acetate tetrahydrate are dissolved in a mixed solution of 7.5mL of ethanol, 2mL of water and 0.5mL of glacial acetic acid, then 1.9g of polyvinylpyrrolidone (Kw = 1300000) is added, and the mixture is magnetically stirred for 20min under the hydrothermal condition of 55 ℃ to obtain a homogeneous sol-like precursor which is collected by a medical registry. And (3) taking a commercial cotton candy machine, regulating the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotor at a constant speed, ejecting precursor fibers from small holes in the side surface of the rotor under the action of centrifugal force, and collecting the precursor fibers at a position 13.5cm away from the rotor by using a collecting rod. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in air atmosphere, heating the fibers from room temperature to 300 ℃ at the temperature of 2 ℃/min, calcining the fibers for 1h,heating to 550 deg.C for 20min, calcining at 550 deg.C for 6 hr, and cooling to room temperature to obtain K 0.5 MnO x A hollow nanotube catalyst.
K 0.5 MnO x The XRD pattern of the hollow nanotube catalyst is shown in FIG. 2, from which it can be seen that the catalyst has a significant K 2-x Mn 8 O 16 Indicating that the crystalline phase of manganese is altered by the incorporation of K. The SEM photograph is shown in FIG. 4, and the catalyst has a hollow nanotube structure with an average diameter of 2.46 μm. The activity of the catalyst for catalytic combustion of soot particles is shown in table 2.
Example 9
Preparation of K 0.5 CoO x Nanotube-structured catalyst
0.294g of potassium acetate and 2.99g of cobalt acetate tetrahydrate are dissolved in a mixed solution of 7.5mL of ethanol, 2mL of water and 0.5mL of glacial acetic acid, then 2.1g of polyvinylpyrrolidone (Kw = 1300000) is added, and magnetic stirring is carried out for 20min under the hydrothermal condition of 55 ℃ to obtain a homogeneous sol-like precursor, which is collected by a medical registry. And (3) taking a commercial cotton candy machine, regulating the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotor at a constant speed, ejecting precursor fibers from small holes in the side surface of the rotor under the action of centrifugal force, and collecting the precursor fibers at a position 13.5cm away from the rotor by using a collecting rod. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in an air atmosphere, raising the temperature from room temperature to 300 ℃ at a rate of 2 ℃/min, calcining the fibers for 1h, raising the temperature to 550 ℃ at a rate of 20min, calcining the fibers at 550 ℃ for 6h, and then lowering the temperature to room temperature to obtain K 0.5 CoO x A hollow nanotube catalyst.
K 0.5 CoO x The XRD pattern of the hollow nanotube catalyst is shown in FIG. 2, from which it can be seen that the catalyst has significant Co 3 O 4 Characteristic diffraction peaks of (2), which indicates that Co is a cause of the diffraction 3 O 4 Has a large lattice spacing, K has been doped to Co 3 O 4 In the crystal lattice of (1). The SEM photograph is shown in FIG. 4, and the catalyst has a hollow nanotube structure with an average diameter of 3.16 μm. The catalyst catalyzes and burns soot particlesThe activity of (A) is shown in Table 2.
Example 10
Preparation of MnCoO x Nanotube structured catalyst
2.451g of manganese acetate tetrahydrate and 2.491g of cobalt acetate tetrahydrate were dissolved in a mixed solution of 7.5mL of ethanol, 2mL of water and 0.5mL of glacial acetic acid, and then 1.9g of polyvinylpyrrolidone (Kw = 1300000) was added, and magnetic stirring was performed at 55 ℃ under hydrothermal conditions for 20min to obtain a homogeneous sol-like precursor, which was collected by a medical registry. And (3) taking a commercial cotton candy machine, regulating the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotor at a constant speed, ejecting precursor fibers from small holes in the side surface of the rotor under the action of centrifugal force, and collecting the precursor fibers at a position 13.5cm away from the rotor by using a collecting rod. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in an air atmosphere, raising the temperature from room temperature to 300 ℃ at a speed of 2 ℃/min, calcining the fibers for 1h, raising the temperature to 550 ℃ at 20min, calcining the fibers at 550 ℃ for 6h, and then lowering the temperature to room temperature to obtain MnCoO x A hollow nanotube catalyst.
MnCoO x The XRD pattern of the hollow nanotube catalyst is shown in FIG. 2, from which it can be seen that the catalyst has significant CoMn 2 O 4 Characteristic diffraction peaks of spinel. The SEM photograph is shown in FIG. 4, and the catalyst has a hollow nanotube structure with an average diameter of 2.43 μm. The activity of the catalyst for catalytic combustion of soot particles is shown in table 2.
Example 11
Preparation K 0.5 MnCoO x Nanotube structured catalyst
2.491g of potassium acetate, 2.451g of manganese acetate tetrahydrate and 2.491g of cobalt acetate tetrahydrate were dissolved in a mixed solution of 7.5mL of ethanol, 2mL of water and 0.5mL of glacial acetic acid, and then 1.9g of polyvinylpyrrolidone (Kw = 1300000) was added thereto, followed by magnetic stirring at 55 ℃ under hydrothermal conditions for 20min to obtain a homogeneous sol-like precursor, which was collected by a medical registry. Taking a commercial cotton candy machine, adjusting the rotating speed to 4000rpm at room temperature, slowly pushing the precursor sol in the medical injector into the rotating head at a constant speed, centrifuging the precursorThe precursor fibers were ejected from small holes in the side of the rotor under force and collected with a collector bar at a distance of 13.5cm from the rotor. Drying the collected fibers at 80 ℃ for 24h, calcining the fibers in a muffle furnace in an air atmosphere, raising the temperature from room temperature to 300 ℃ at a rate of 2 ℃/min, calcining the fibers for 1h, raising the temperature to 550 ℃ at a rate of 20min, calcining the fibers at 550 ℃ for 6h, and then lowering the temperature to room temperature to obtain K 0.5 MnCoO x A hollow nanotube catalyst.
K 0.5 MnCoO x The XRD pattern of the hollow nanotube catalyst is shown in FIG. 2, from which it can be seen that the catalyst has a significant K 2 Mn 4 O 8 Characteristic diffraction peak of (1). The SEM photograph is shown in FIG. 4, and the catalyst is in the form of hollow nanotube structure with average diameter of 1.98 μm. The activity of the catalyst for catalytic combustion of soot particles is shown in table 2.
TABLE 2 catalytic combustion of soot particles with composite metal oxide catalyst with nanotube structure
Example 12
Method for evaluating catalyst activity: the gas chromatography detection system is utilized, and the catalyst adopts a fixed bed mode.
The method comprises the following specific steps: respectively placing the nanotube metal oxide catalyst and the soot particles with the mass ratio of 10 2 The volume content of (A) is 10%, and the balance gas is Ar; the heating rate is controlled to be about 2 ℃/min.
Evaluation method: the oxidation capacity of the catalyst is expressed by the combustion temperature of soot particles, wherein the soot particlesIgnition temperature (T) of object 10 ) Temperature (T) corresponding to the maximum combustion rate 50 ) And burnout temperature (T) 90 ) Respectively representing the temperature points corresponding to 10%, 50% and 90% of the soot combustion, by calculating the CO generated by soot combustion in the temperature programmed oxidation reaction 2 Integration of the curve with CO, CO 2 The temperature points corresponding to the numerical values of 10%, 50% and 90% of the sum of the integrated areas of CO are T 10 、T 50 And T 90 . Wherein S CO2 m Indicates the CO corresponding to the catalyst at the time of maximum soot burning rate 2 And (4) selectivity. The catalytic combustion results of the pure soot particles are shown in table 3, and it can be seen from the table that the combustion temperature of the pure soot is higher in the absence of the catalyst, which indicates that the nanotube metal oxide catalyst prepared by the present invention has higher catalytic activity for catalytic combustion of the soot particles.
TABLE 3 catalytic Combustion Activity of pure soot particles
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (7)
1. A metal oxide catalyst with a hollow nanotube structure, which is characterized in thatIs a single metal oxide catalyst with a nanotube structure, which is prepared from a single metal: manganese, iron, cobalt, nickel, copper, lanthanum, cerium and oxygen, expressed as: mnO x 、FeO x 、CoO x 、NiO x 、CuO x 、LaO x 、CeO x (ii) a Or the catalyst is a composite metal oxide catalyst with a nanotube structure, and is prepared from composite metal: potassium manganese, potassium cobalt, manganese cobalt, potassium manganese cobalt and oxygen.
2. The hollow nanotube structure metal oxide catalyst of claim 1, wherein the catalyst is a nanotube structure composite metal oxide catalyst: k 0.5 MnO x 、K 0.5 CoO x 、MnCoO x 、K 0.5 MnCoO x 。
3. A process for preparing the catalyst of claims 1-2, comprising: the metal oxide catalyst is prepared from metal nitrate, metal acetate, glacial acetic acid and polyethylene pyrrolidone serving as raw materials through dissolution, centrifugal spinning, drying and roasting.
4. The method for preparing the catalyst according to claim 3, wherein the polyvinylpyrrolidone has an average molecular weight of 1300000 and a polymerization degree of K =88-96.
5. The method for preparing the catalyst according to claim 3, which specifically comprises: weighing a certain amount of metal nitrate and metal acetate according to a stoichiometric ratio, dissolving the metal nitrate and the metal acetate in ethanol and water, adding a glacial acetic acid solution, adding polyvinylpyrrolidone after uniformly stirring, stirring for 20min at 25-70 ℃ under a water bath condition to obtain a homogeneous transparent sol precursor, and collecting the precursor by using a medical injector;
slowly injecting the collected precursor solution into a centrifuge of a centrifugal spinning device, and collecting at a position 13.5cm away from the centrifuge at the rotating speed of 1000-4000rpm to obtain precursor fibers;
and drying the collected fibers in an oven at 80 ℃ for 24 hours, and calcining the dried fibers in a muffle furnace to obtain the metal oxide catalyst.
6. The method for preparing the catalyst according to claim 3, wherein the calcination is performed by raising the temperature to 300 ℃ in a muffle furnace at a rate of 2 ℃/min, maintaining the temperature for 1 hour, raising the temperature to 550 ℃ within 20min, and calcining the catalyst at 550 ℃ for 6 hours.
7. The application of the metal oxide catalyst with the hollow nanotube structure is characterized in that the catalyst is applied to catalytic combustion reaction of soot particles in tail gas of a diesel engine.
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