CN115845868A - Three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device and preparation method and application thereof - Google Patents
Three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device, and a preparation method and application thereof, and relates to the technical field of environmental catalysis. The high-entropy perovskite monolithic catalytic device comprises a substrate (a honeycomb ceramic substrate) and a high-entropy perovskite oxide; the high-entropy perovskite oxide is loaded on the surface of the substrate; the high-entropy perovskite oxide is of a three-dimensional ordered macroporous structure; the chemical formula of the high-entropy perovskite oxide is ABO 3 Wherein, the element A is selected from one or more of Ca, K, la, sr, bi, gd, nd, sm and Y; b element is selected from Cr, mn,Fe. One or more of Co, ni, cu, ti and Al; at least one of the element A or the element B is composed of five or more elements. The three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device prepared by the invention has a three-dimensional ordered macroporous structure, so that the catalyst has good mass transfer diffusion performance and catalytic oxidation activity.
Description
Technical Field
The invention relates to the technical field of environmental catalysis, in particular to a three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device and a preparation method and application thereof.
Background
The development of new catalytic materials may bring breakthrough progress and revolutionary changes to the technical field of environmental catalysis, and the assisted environmental catalysis (such as the catalytic purification of soot particles of diesel vehicles, the catalytic purification of coal mine gas methane, and the catalytic combustion of industrial VOCs) has important economic, environmental and social meanings. High-entropy materials have been rapidly developed in recent years, and have been increasingly widely used due to their unique structures and excellent properties in various fields. The high-entropy material is a material composed of at least 5 chemical elements with equal molar ratio or close to equal molar ratio, and the high-entropy perovskite is a high-entropy perovskite structure formed by a plurality of cations occupying different positions of crystal lattices under the high-entropy concept. The high-entropy material has four characteristics: thermodynamic high entropy effect, lattice distortion effect, kinetic delayed diffusion effect, and cocktail effect. The high-entropy material has a plurality of compositions, and the difference between the radius and the binding energy of each atom is more obvious than that of the traditional material, so that the high-entropy material shows a more obvious lattice distortion phenomenon than that of the traditional material, and has a kinetic delayed diffusion phenomenon and an anti-grain coarsening behavior. Therefore, the high-entropy material used as a catalyst shows higher stability than the traditional material, and is more suitable for the field of high-temperature thermocatalysis. However, the existing high-entropy material catalyst generally has the problem of low catalyst contact efficiency, and the catalytic activity of the catalyst needs to be further improved.
Disclosure of Invention
The invention aims to provide a three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device, a preparation method and application thereof, which are used for solving the problems in the prior art, and the high-entropy perovskite monolithic catalytic device is prepared into a three-dimensional ordered macroporous structure by utilizing a simple one-step preparation process, so that the mass transfer diffusion performance of the catalytic device is improved, and the catalytic activity of the catalytic device is improved.
In order to achieve the purpose, the invention provides the following scheme:
in one technical scheme of the invention, the high-entropy perovskite monolithic catalytic device comprises a substrate and a high-entropy perovskite oxide;
the high-entropy perovskite oxide is loaded on the surface of the substrate;
the high-entropy perovskite oxide is of a three-dimensional ordered macroporous structure;
the chemical formula of the high-entropy perovskite oxide is ABO 3 Wherein, the element A is selected from one or more of Ca, K, la, sr, bi, gd, nd, sm and Y; b element is selected from one or more of Cr, mn, fe, co, ni, cu, ti and Al; at least one of the elements A and B is composed of five or more elements in an equimolar ratio.
Further, the loading of the entropy perovskite oxide catalyst is 1-20wt%.
Further, the substrate is a ceramic substrate with a honeycomb structure or a metal alloy substrate, and the substrate is a cylinder, a cuboid or a cube; the diameter of the cylinder is 5-100cm, the height is 2-100cm, the length and the width of the cuboid or the cube are 5-100cm respectively, and the height is 2-100cm; the aperture of the three-dimensional ordered macroporous structure is 0.5-2 mu m, and the porosity is 1-20%. Preferably, the substrate is a ceramic substrate.
In the second technical scheme of the invention, the preparation method of the high-entropy perovskite monolithic catalytic device comprises the following steps:
adding a salt containing an element A and a salt containing an element B into water for dissolving, and then adding an organic acid and an organic solvent to obtain mixed metal salt sol;
adding a polystyrene microsphere dispersion liquid into the mixed metal salt sol to obtain a mixed dispersion liquid;
and (3) soaking a matrix in the mixed dispersion liquid, and drying and calcining after the soaking to obtain the high-entropy perovskite integral catalytic device.
Further, the concentration of the mixed metal salt sol is 0.2mol/L-2.2mol/L.
Further, the salt containing the A element is nitrate of the A element; the salt containing the B element is nitrate of the B element; the organic acid is oxalic acid, citric acid or tartaric acid; the organic solvent is ethylene glycol; the polystyrene microsphere dispersion is polystyrene microsphere ethylene glycol dispersion.
Further, the concentration of the polystyrene microsphere dispersion liquid is 10g/L; the ratio of the total mass of the salt containing the A element and the salt containing the B element to the mass of the polystyrene microspheres is 5:1.
further, the time for the immersion is 5 to 20 hours; the drying is specifically drying for 10-30 hours at 50 ℃; the calcination is specifically calcination at 800 ℃ for 20-30 hours. The drying and calcining time is favorable for generating a three-dimensional ordered macroporous structure, and a single-phase high-entropy perovskite is formed, so that no phase separation occurs, and the high-temperature resistance and the mass transfer diffusion performance of the catalytic material can be effectively improved. Ranges above or below the above-noted ranges all affect the formation of three-dimensional ordered macroporous structures, as well as single-phase high-entropy perovskites.
In the third technical scheme of the invention, the high-entropy perovskite monolithic catalytic device is applied to a diesel vehicle exhaust particulate trap.
In the fourth technical scheme of the invention, the high-entropy perovskite monolithic catalytic device is applied to catalytic combustion purification of VOCs in the coal chemical industry, and the temperature for catalytic combustion purification is 150-400 ℃.
The fifth technical scheme of the invention is that the high-entropy perovskite monolithic catalytic device is applied to catalytic combustion purification of coal mine ventilation gas methane, and the temperature of the catalytic combustion purification is 350-600 ℃.
The invention discloses the following technical effects:
(1) The invention discloses a simple preparation method of a high-entropy perovskite monolithic catalytic device with a three-dimensional ordered macroporous structure, which comprises the steps of firstly preparing a metal sol dispersion liquid containing PS microspheres, then coating the metal sol dispersion liquid on a honeycomb (ceramic) substrate, and finally calcining to remove a carbon template to prepare the high-entropy perovskite catalytic device with the three-dimensional ordered macroporous structure. The preparation method is simple and easy for industrial macro-quantitative preparation, and realizes the simple one-step preparation of the three-dimensional ordered macroporous structure high-entropy catalyst.
(2) The three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device prepared by the invention has a three-dimensional ordered macroporous structure, so that the catalyst has good mass transfer diffusion performance and catalytic oxidation activity. In addition, the three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device has higher configuration entropy, and endows the catalyst with severe lattice distortion and rich defects, so that the catalyst has excellent catalytic combustion activity and stability (has good high temperature resistance, moisture resistance and sulfur resistance).
(3) The catalyst has low cost of active ingredients, good economical efficiency, and great economic and environmental benefits when popularized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a pictorial representation, scanning electron micrograph, X-ray diffraction (XRD) and EDS-Mapping profile of HEPO of the catalytic device prepared in example 1; wherein, a is a real object picture, b is a scanning electron microscope picture, c is an X-ray diffraction picture, and d is an EDS-Mapping picture;
FIG. 2 is a graph of the combustion performance of the catalytic device prepared in example 2 for catalyzing soot particulates;
FIG. 3 is a graph of the combustion performance of catalytic methane of the catalytic device prepared in example 3;
FIG. 4 is a graph of the combustion performance of the catalytic device prepared in example 4 for catalyzing propylene;
FIG. 5 is a macro-scale preparation diagram of the catalytic device of example 3;
FIG. 6 is the thermal stability and moisture resistance of the catalytic device prepared in example 3;
FIG. 7 is a graph showing the methane combustion performance of the catalytic devices prepared in example 3 and comparative examples 1 and 2;
FIG. 8 is the cycle stability of the catalytic device prepared in example 3;
FIG. 9 is a graph of the combustion performance of the catalytic device prepared in example 3 and other different configurations of entropy catalytic devices for catalyzing methane.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
The size of the honeycomb ceramic substrate used in the examples of the present invention and the comparative examples was 1.4 × 1.4 × 1.5cm, and other sizes were also able to achieve the technical effects of the present invention.
Example 1
2g of lanthanum nitrate hexahydrate, 0.4g of nickel nitrate nonahydrate, 0.41g of manganese nitrate tetrahydrate, 0.45g of iron nitrate nonahydrate, 0.56g of cobalt nitrate hexahydrate and 0.16g of copper nitrate hexahydrate are placed in a 200mL beaker, 100mL of distilled water is added, and the solid is completely dissolved under the ultrasonic action. 1.250g of citric acid monohydrate solid and 0.307g of ethylene glycol liquid were added and stirred on a magnetic stirrer for 10 minutes to obtain a mixed metal salt sol. Adding 3mL of PS (polystyrene) microsphere ethylene glycol dispersion liquid with the concentration of 10g/L into the mixed metal salt sol, and stirring for 24 hours to obtain the dispersion liquid. The honeycomb ceramic substrate is placed in the dispersion liquid for dipping and coating for 24 hours, taken out and dried for 12 hours at 60 ℃, and then calcined for 10 hours at 900 ℃ to prepare the three-dimensional ordered macroporous high-entropy perovskite (3 DOMLa (NiMnFeCoCu) O 3 ) Monolithic catalytic devices (abbreviation: catalytic device, 3 domepo), catalyst loading 4%, pore size 0.5-2 μm, porosity 3%.
The physical map, the scanning electron microscope map, the X-ray diffraction pattern (XRD) and the EDS-Mapping map of HEPO of the catalytic device prepared in the example are shown in figure 1; in the figure, a is a real object picture, b is a scanning electron microscope picture, c is an X-ray diffraction picture, and d is an EDS-Mapping map. From fig. 1, it can be seen that the catalytic device prepared by the present example has the micro-morphology feature of the three-dimensional ordered macroporous structure. No phase separation occurred in the XRD pattern, further demonstrating the successful preparation of High Entropy Perovskite Oxide (HEPO).
Example 2
Taking 2.2g of lanthanum nitrate hexahydrate, 0.4g of chromium nitrate nonahydrate and 0.41g of nitrate tetrahydrateManganese acid, 0.45g of ferric nitrate nonahydrate, 0.56g of bismuth nitrate hexahydrate and 0.13g of copper nitrate hexahydrate are placed in a 500mL beaker, 200mL of distilled water is added, and the solid is completely dissolved under the action of ultrasound. 1.240g of citric acid monohydrate solid and 0.307g of ethylene glycol liquid were added and stirred on a magnetic stirrer for 10 minutes to obtain a mixed metal salt sol. Adding 3mL of PS microsphere ethylene glycol dispersion liquid with the concentration of 10g/L into the mixed metal salt sol, and stirring for 20 hours to obtain the dispersion liquid. The honeycomb ceramic substrate is placed in the dispersion liquid for dipping and coating for 24 hours, taken out and dried at 70 ℃ overnight, and then calcined at 800 ℃ for 10 hours to prepare the three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device 3DOMLa (CrMnFeCuBi) O 3 (short for: catalytic device, 3 DOMHEPO), the catalyst loading is 10%, the pore diameter is 0.5-2 μm, and the porosity is 3%.
The catalytic device prepared in the embodiment is used for evaluating and verifying the catalytic combustion performance of soot particulate matters in the tail gas of a diesel vehicle, and the evaluation method comprises the following steps:
the catalyst sample soot catalytic oxidation activity test was performed in a fixed bed microreactor at atmospheric pressure. The reactor is made of a quartz tube, the inner diameter of the reactor is 6.4mm, the temperature rise program and the temperature rise rate are automatically controlled by a set program, and the test temperature rise program is as follows: room temperature → 200 ℃, and the retention time is 30min;200 ℃→ 700 ℃, and the rate of temperature rise is 2 ℃/min; and finally staying at 700 ℃ for 30min. The root selected for the experiment is rhombohedral carbon black particles, and the specific root load operation is as follows: dissolving a certain amount of root in an ethylene glycol solution to obtain a 12mg/mL suspension, sucking a certain amount of suspension by using a liquid transfer gun, uniformly dripping the suspension on a sample to be tested, drying at 200 ℃, simulating a loose contact mode, and keeping the mass ratio of a catalyst to the root at 10/1. Subsequently, the sample loaded with the root is wrapped with a quartz cotton pad and placed in a constant temperature area of the reaction tube. The reaction gas composition (volume fraction) was: 10% of 2 ，90％N 2 The total flow rate of gas was 50mL/min.
The gas content after the reaction is analyzed on line by a FuliGC-9790 type gas chromatograph, FID is a detector, high-purity nitrogen is used as carrier gas, the temperature of the column furnace is 90 ℃, the temperature of the detector is 150 ℃, and the auxiliary temperature is 350 ℃. The relative peak area of the chromatogram is used to represent the relative content of a certain gas. Catalytic converterThe performance properties were evaluated with T10 and T50, respectively, i.e. corresponding to the temperatures at which the root conversion was 10% and 50%, respectively. The conversion of Soot was calculated as: conversion of a certain temperature and the root corresponding to the previous temperature into CO x Peak area divided by the conversion of root to CO during the entire reaction x Sum of peak areas of (a).
The test results are shown in FIG. 2, where T is 90 Which indicates the temperature required for the soot conversion to reach 90%, it can be seen from fig. 2 that the catalytic device prepared in example 2 exhibited a good soot catalytic combustion activity, and the soot was completely oxidized at 550 c, and the catalyst was completely regenerated.
Example 3
0.5g of lanthanum nitrate hexahydrate, 0.11g of calcium nitrate, 0.11g of strontium nitrate, 0.12g of potassium nitrate, 0.02g of bismuth nitrate, 0.4g of chromium nitrate nonahydrate, 0.41g of manganese nitrate tetrahydrate, 0.45g of iron nitrate nonahydrate, 0.56g of cobalt nitrate hexahydrate and 0.13g of nickel nitrate hexahydrate are placed in a 500mL beaker, 190mL of distilled water is added, and the solid is completely dissolved under the action of ultrasound. 1.140g of oxalic acid monohydrate solid and 1.407g of ethylene glycol liquid were added and stirred on a magnetic stirrer for 60 minutes to obtain a mixed metal salt sol. Adding 10mL of PS microsphere ethylene glycol dispersion liquid with the concentration of 10g/L into the mixed metal salt sol, and stirring for 1 hour to obtain the dispersion liquid. Dipping and coating the honeycomb ceramic substrate in the dispersion for 1 hour, taking out the honeycomb ceramic substrate, drying the honeycomb ceramic substrate at 80 ℃ overnight, calcining the honeycomb ceramic substrate at 900 ℃ for 20 hours, and finally preparing the three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device 3DOM (LaCaSrKBi) (CrMnFeCoNi) O containing 10 elements 3 (short for: catalytic device, 3 DOMHEPO), the catalyst loading is 10%, the pore diameter is 0.5-2 μm, and the porosity is 3%.
The catalytic device prepared in the embodiment is used for evaluating and verifying the catalytic combustion performance of coal mine gas methane, and the evaluation method comprises the following steps:
CH 4 the catalytic combustion activity was evaluated by simulating a fixed bed reactor with a quartz tube. The catalyst sample to be tested was loaded in the middle of a quartz tube. The quartz tube is arranged in the tube furnace, and after the quartz tube is connected with the gas circuit and the leakage is detected, a temperature rise program is set: heating to 25 deg.C for 30 min-250 deg.C, holding for 25min, heating to 300 deg.C at a rate of 10 deg.C/min, and holding for 25minThe temperature rise speed and the heat preservation time are respectively 350-750 ℃. Simulated air passing through the catalyst at a total gas flow of 50mL/min, 1% CH 4 、5％O 2 And 94% of N 2 . The off-gas composition of the catalytic reaction was monitored on-line in real time by gas chromatography (GC-9790). The instrument setup conditions for the GC were: the carrier gas is N 2 Hydrogen Flame Ionization Detector (FID) was used, and the column furnace temperature was 70 ℃. CH (CH) 4 The calculation formula for the conversion is:
wherein X in the formula methane Representing the conversion of methane, F methane,in Represents the inlet concentration of methane, F methane,out Represents the exit concentration of methane after catalytic oxidation, F methane,in -F methane,out Indicating the concentration of methane converted during the catalytic oxidation. T is 90 Represents the temperature at which the methane conversion is 90%.
The test results are shown in FIG. 3, where round1 indicates the 1 st round of catalyst usage, round2 indicates the 2 nd round of catalyst usage, and round3 indicates the 3 rd round of catalyst usage. It can be seen from fig. 3 that the catalytic device prepared in example 3 exhibited good catalytic combustion activity of methane, and methane was completely oxidized at 600 ℃. And the catalyst shows good high-temperature stability, and the activity is not reduced after the catalyst is used for 50 hours.
FIG. 6 is the thermal stability and moisture resistance of the catalytic device prepared in example 3; as can be seen from FIG. 6, the high-entropy perovskite prepared in example 3 can maintain good catalytic activity under the conditions of heat aging in an air atmosphere at 800 ℃ and 10% humidity, and the catalyst catalyzes CH at 450 DEG C 4 Oxidation to CO 2 The conversion rate is not substantially reduced.
FIG. 8 is the cycle stability of the catalytic device prepared in example 3; as can be seen from FIG. 8, the three-dimensional ordered macroporous high-entropy perovskite catalytic device (3 DOMHEPO) prepared in example 3 catalyzes CH after being recycled for 20 times 4 Oxidation to CO 2 Catalytic combustion activity does not occurAnd (4) descending.
Example 4
1g of lanthanum nitrate hexahydrate, 0.4g of chromium nitrate nonahydrate, 0.41g of manganese nitrate tetrahydrate, 0.45g of iron nitrate nonahydrate, 0.56g of bismuth nitrate hexahydrate and 0.16g of copper nitrate hexahydrate are placed in a 200mL beaker, 100mL of distilled water is added, and the solid is completely dissolved under the action of ultrasound. 1.450g of oxalic acid monohydrate solid and 0.307g of ethylene glycol liquid are added, and the mixture is stirred on a magnetic stirrer for 10 minutes to prepare mixed metal salt sol. And adding 20ml of PS microsphere ethylene glycol dispersion liquid with the concentration of 10g/L into the mixed metal salt sol, and stirring for 24 hours to obtain the dispersion liquid. The honeycomb ceramic substrate is placed in the dispersion liquid for dipping and coating for 10 hours, taken out and dried at 100 ℃ overnight, and then calcined at 760 ℃ for 10 hours to finally prepare the three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device 3DOMLa (CrMnFeBiCu) O 3 (for short: catalytic device, 3 DOMHEPO), the catalyst loading is 10%, the pore diameter is 0.5-2 μm, and the porosity is 4%.
The catalytic device prepared in the embodiment is evaluated and verified for the catalytic combustion performance of VOCs (propylene), and the evaluation method comprises the following steps: c of catalyst sample 3 H 8 The catalytic oxidation activity was evaluated by simulating a fixed bed reactor with a quartz tube. Filling a catalyst sample to be tested in the middle of a quartz tube, wherein the temperature programming process comprises the following steps: heat from 200 ℃ to 700 ℃ (5 ℃/min; 50 ℃/segment interval), each temperature segment held for 30 minutes. The composition of the reaction gas was 3000ppm C 3 H 8 、12％O 2 And N 2 Balance, total flow rate is 50mL/min, corresponding mass space velocity is about 37500mLg -1 h -1 . The tail gas components of the catalytic reaction are subjected to real-time online monitoring on the tail gas by a gas chromatography (GC-9790 type) of Fuli corporation in Taizhou, N 2 Is a carrier gas. The instrument setup conditions for GC-9790 were: the carrier gas is N 2 The concentration of propane was expressed as a relative content by a chromatogram using a hydrogen Flame Ionization Detector (FID), a column furnace temperature of 90 deg.C, a detection temperature of 150 deg.C, a sample injection temperature of 200 deg.C. Wherein, C 3 H 8 The calculation formula for the conversion is:
wherein, X in the formula Propylene (PA) Representing the conversion of propylene, F Propylene, in Represents the inlet concentration of propylene, F Propylene, out Represents the outlet concentration of propylene after catalytic oxidation, F Propylene, in -F Propylene, out Indicating the concentration of propylene converted during the catalytic oxidation.
The test results are shown in fig. 4, and it can be seen from fig. 4 that the catalytic device prepared in example 4 shows better catalytic combustion activity of propylene, and propylene is completely oxidized at 300 ℃. And the catalyst shows good high-temperature stability, and the activity is not reduced after 50 hours of use.
Comparative example 1
La(Mn 0.2 Fe 0.2 Ni 0.2 Cu 0.2 Co 0.2 )O 3 The preparation method of the @ PAC monolithic catalyst comprises the following steps:
dissolving 1mmol of citric acid in 5mL of absolute ethanol, stirring until the citric acid is completely dissolved, then respectively weighing 1mmol of lanthanum nitrate, 0.2mmol of cobalt nitrate, 0.2mmol of manganese nitrate, 0.2mmol of ferric nitrate, 0.2mmol of nickel nitrate and 0.2mmol of copper nitrate, respectively adding the lanthanum nitrate, the cobalt nitrate, the manganese nitrate, the ferric nitrate, the nickel nitrate and the copper nitrate into the solution, stirring until the solution is clear, and then continuously stirring for 0.5h to obtain a precursor solution. 5mL of precursor solution is transferred by a liquid transfer gun and is dripped on a substrate material, the substrate material is kept stand at room temperature for 0.5h, dried in a blast drying oven at 80 ℃ for 2h, and then calcined in a muffle furnace at 600 ℃ for 3h to obtain the high-entropy perovskite monolithic catalyst La (Mn) with 0.6 percent of active component loading 0.2 Fe 0.2 Ni 0.2 Cu 0.2 Co 0.2 )O 3 @PAC。
Comparative example 2
La(Mn 0.2 Fe 0.2 Ni 0.2 Cu 0.2 Co 0.2 )O 3 The preparation method of the @ PAC three-dimensional ordered macroporous monolithic catalyst comprises the following steps:
dissolving 1mmol of citric acid in 5mL of absolute ethanol, stirring until the citric acid is completely dissolved, and then weighing 1mmol of lanthanum nitrate, 0.2mmol of cobalt nitrate and 0.2m of lanthanum nitrate respectivelyAnd respectively adding mol of manganese nitrate, 0.2mmol of ferric nitrate, 0.2mmol of nickel nitrate and 0.2mmol of copper nitrate into the solution, stirring until the solution is clear, continuing stirring for 0.5h to obtain a precursor solution, adding 20ml of PS microsphere ethylene glycol dispersion liquid with the concentration of 10g/L into the precursor solution, and stirring for 24 h to obtain the dispersion liquid. 5mL of dispersion liquid is transferred by a liquid transfer gun and is coated on a substrate material, after the dispersion liquid is kept stand for 0.5h at room temperature, the dispersion liquid is dried for 2h at 80 ℃ in a blast drying oven, and then the dispersion liquid is placed in a muffle furnace for calcining for 3h at 600 ℃ to obtain the three-dimensional ordered macroporous high-entropy perovskite monolithic catalyst 3DOM La (Mn) with 0.6 percent of active component loading 0.2 Fe 0.2 Ni 0.2 Cu 0.2 Co 0.2 )O 3 @PAC。
FIG. 5 is a macro-scale preparation diagram of the catalytic device of example 3;
fig. 7 is a graph showing the combustion performance of catalytic methane in the catalytic devices prepared in example 3 and comparative examples 1 and 2, and it can be seen from fig. 7 that the catalytic combustion activity of the catalytic device prepared in example 3 is high, and the catalytic methane combustion T90 is 500 ℃, while the catalytic methane combustion T90 of the catalytic device in comparative example 1 is 700 ℃ and the catalytic methane combustion T90 of the catalytic device in comparative example 2 is about 600 ℃. The three-dimensional ordered macroporous structure of the high-entropy catalytic device has a remarkable promoting effect on catalytic activity, and the large configuration entropy of various elements selected by the high-entropy catalytic device plays a promoting effect on the activity of a catalyst. The three-dimensional ordered macroporous structure and the high-entropy structure act together, so that the catalytic conversion temperature T90 of the catalyst is obviously reduced (700 ℃ → 500 ℃).
FIG. 9 is a graph of the performance of catalytic devices prepared in example 3 to catalyze the combustion of methane with other entropy catalytic devices of different configurations; it can be seen from figure 9 that the high entropy catalytic device to which the present invention relates exhibits better catalytic combustion activity than conventional low and medium entropy perovskites. With increasing entropy of configuration, the T90 conversion temperature of the catalyst drops significantly (700 ℃ → 500 ℃).
Catalyst for catalytic oxidation of motor vehicle tail gas (CO, NO, CH) x Root), its catalytic activity is influenced by both the efficiency of the contact of the reactants with the catalyst and the intrinsic activity of the active sites of the catalyst. Surface emission of catalystThe mass transfer and diffusion processes of the raw reactants can have a significant effect on the performance of the catalyst. The three-dimensional ordered macroporous structure is prepared on the integral catalytic device, so that the contact efficiency of reactants and the catalyst is improved, and the reaction activity of the catalyst is improved.
So far, the research of high-entropy materials still stays in a laboratory stage, and a mild and feasible preparation method which is easy to amplify is lacked. The invention provides a mild, feasible and easily-amplified preparation method (as shown in figure 5), and an integral high-entropy perovskite catalytic device with a three-dimensional ordered macroporous microstructure is synthesized, is used for the field of environmental thermocatalysis, and has a good catalytic oxidation effect.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A high entropy perovskite monolithic catalytic device, characterized in that it comprises a substrate and a high entropy perovskite oxide;
the high-entropy perovskite oxide is loaded on the surface of the substrate;
the high-entropy perovskite oxide is of a three-dimensional ordered macroporous structure;
the chemical formula of the high-entropy perovskite oxide is ABO 3 Wherein, the element A is selected from one or more of Ca, K, la, sr, bi, gd, nd, sm and Y; b element is selected from one or more of Cr, mn, fe, co, ni, cu, ti and Al; at least one of the elements A and B is composed of five or more elements in an equimolar ratio.
2. A high entropy perovskite monolithic catalytic device as claimed in claim 1, wherein the loading of the high entropy perovskite oxide is between 1 and 20wt%.
3. A high entropy perovskite monolithic catalytic device as claimed in claim 1, wherein said substrate is a ceramic or metal alloy substrate of honeycomb structure; the aperture of the three-dimensional ordered macroporous structure is 0.5-2 μm, and the porosity is 1-20%.
4. A method of making a high entropy perovskite monolithic catalytic device as claimed in claim 1 comprising the steps of:
adding salt containing an element A and salt containing an element B into water for dissolving, and then adding organic acid and an organic solvent to obtain mixed metal salt sol;
adding a polystyrene microsphere dispersion liquid into the mixed metal salt sol to obtain a mixed dispersion liquid;
and (3) dipping a matrix in the mixed dispersion liquid, and drying and calcining after dipping to obtain the high-entropy perovskite monolithic catalytic device.
5. The production method according to claim 4, wherein the salt containing the element A is a nitrate of the element A; the salt containing the B element is nitrate of the B element; the organic acid is oxalic acid, citric acid or tartaric acid; the organic solvent is ethylene glycol; the polystyrene microsphere dispersion is polystyrene microsphere ethylene glycol dispersion.
6. The method according to claim 4, wherein the polystyrene microsphere dispersion has a concentration of 10g/L; the ratio of the total mass of the salt containing the element A and the salt containing the element B to the mass of the polystyrene microspheres is 5.
7. The method according to claim 4, wherein the time for the immersion is 24 hours; the drying is specifically drying for 20 hours at 50 ℃; the calcination is specifically calcination at 800 ℃ for 48 hours.
8. Use of the high-entropy perovskite monolithic catalytic device of claim 1 in the preparation of a diesel exhaust particulate trap.
9. The application of the high-entropy perovskite monolithic catalytic device in catalytic combustion purification of VOCs in coal chemical industry according to claim 1, wherein the temperature of catalytic combustion purification is 150-400 ℃.
10. The use of a high entropy perovskite monolithic catalytic device as claimed in claim 1 in catalytic combustion purification of coal mine ventilation gas methane, wherein the temperature of catalytic combustion purification is in the range of 350-600 ℃.
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