CN115845868B - A three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device and its preparation method and application - Google Patents
A three-dimensional ordered macroporous high-entropy perovskite monolithic catalytic device and its preparation method and application Download PDFInfo
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- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 44
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- 238000007084 catalytic combustion reaction Methods 0.000 claims description 22
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- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229960002303 citric acid monohydrate Drugs 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
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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 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Catalysts (AREA)
Abstract
The invention discloses a three-dimensional ordered large Kong Gaoshang perovskite integral catalytic device and a preparation method and application thereof, and relates to the technical field of environmental catalysis. The high-entropy perovskite integral type catalytic device comprises a matrix (honeycomb ceramic substrate) and high-entropy perovskite oxide, wherein the high-entropy perovskite oxide is loaded on the surface of the matrix, 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 an element A is one or more of Ca, K, la, sr, bi, gd, nd, sm, Y, an element B is one or more of Cr, mn, fe, co, ni, cu, ti, al, and at least one of the element A and the element B consists of five or more elements. The three-dimensional ordered macroporous structure of the three-dimensional ordered large Kong Gaoshang perovskite monolithic catalytic device prepared by the invention ensures 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 large Kong Gaoshang perovskite integral catalytic device, a preparation method and application thereof.
Background
The development of new catalytic materials can bring breakthrough progress and revolutionary change to the technical field of environmental catalysis, and assist environmental catalysis (such as catalytic purification of soot particles of diesel vehicles, catalytic purification of methane of coal mine gas and catalytic combustion of industrial VOCs) has important economic significance, environmental significance and social significance. The high-entropy material has been rapidly developed in recent years, and has shown excellent performance in various fields by a unique structure thereof, and has been increasingly used. 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 a crystal lattice under the concept of high entropy. The high-entropy material has four characteristics of high entropy effect in thermodynamics, lattice distortion effect, delayed diffusion effect in dynamics and cocktail effect. The high-entropy material has a plurality of elements, and the difference of the radius and the binding energy of each atom is more obvious than that of the traditional material, so that the high-entropy material has more obvious lattice distortion phenomenon than that of the traditional material, so that the high-entropy material has kinetic hysteresis diffusion phenomenon and grain coarsening resistance. Therefore, the high-entropy material used as a catalyst shows higher stability than the traditional material, and is more suitable for the high-temperature thermocatalysis field. 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 large Kong Gaoshang perovskite integral type catalytic device, a preparation method and application thereof, so as to solve the problems in the prior art, and the high-entropy perovskite integral type catalytic device is prepared into a three-dimensional ordered macroporous structure by using a simple one-step preparation process, so that the mass transfer and diffusion performances of the catalytic device are improved, and the catalytic activity of the catalytic device is improved.
In order to achieve the above object, the present invention provides the following solutions:
According to one of the technical schemes, the high-entropy perovskite integral type catalytic device comprises a substrate and high-entropy perovskite oxide;
the high-entropy perovskite oxide is loaded on the surface of the matrix;
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 one or more of Ca, K, la, sr, bi, gd, nd, sm, Y, the element B is one or more of Cr, mn, fe, co, ni, cu, ti, al, and at least one of the element A and the element B consists of five or more elements with equal molar ratio.
Further, the loading of the entropy perovskite oxide catalyst is 1-20wt%.
Further, the matrix is a ceramic matrix or a metal alloy matrix with a honeycomb structure, the matrix is a cylinder, a cuboid or a cube, the diameter of the cylinder is 5-100cm, the height of the cylinder is 2-100cm, the length and the width of the cuboid or the cube are 5-100cm, the height of the cuboid or the cube 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.
The second technical scheme of the invention is that the preparation method of the high-entropy perovskite monolithic catalytic device comprises the following steps:
Adding the salt containing the element A and the salt containing the element B into water for dissolution, and then adding organic acid and organic solvent to obtain mixed metal salt sol;
Adding polystyrene microsphere dispersion liquid into the mixed metal salt sol to obtain mixed dispersion liquid;
and (3) dipping the matrix in the mixed dispersion liquid, and drying and calcining after the dipping is finished to obtain the high-entropy perovskite integral type catalytic device.
Further, the concentration of the mixed metal salt sol is 0.2mol/L-2.2mol/L.
Further, the salt containing the element A is nitrate of the element A, the salt containing the element B is nitrate of the element B, the organic acid is oxalic acid, citric acid or fruit acid, the organic solvent is ethylene glycol, and the polystyrene microsphere dispersion liquid is polystyrene microsphere ethylene glycol dispersion liquid.
Further, the concentration of the polystyrene microsphere dispersion is 10g/L, and the ratio of the sum of the mass of the salt containing the element A and the salt containing the element B to the mass of the polystyrene microsphere is 5:1.
Further, the time of the impregnation is 5-20 hours, the drying is particularly 50 ℃ for 10-30 hours, and the calcining is particularly 800 ℃ for 20-30 hours. The drying and calcining time is favorable for the generation of a three-dimensional ordered macroporous structure and the formation of single-phase high-entropy perovskite, so that phase separation does not occur, and the high temperature resistance and mass transfer diffusion performance of the catalytic material can be effectively improved. Ranges above or below the above-recited range affect the three-dimensional ordered macroporous structure, as well as the formation of single-phase high-entropy perovskite.
The third technical scheme of the invention is the application of the high-entropy perovskite integral catalytic device in a diesel vehicle exhaust particulate matter catcher.
According to the fourth technical scheme, the high-entropy perovskite integral type catalytic device is applied to catalytic combustion purification of VOCs in coal chemical industry, and the temperature of the catalytic combustion purification is 150-400 ℃.
The fifth technical scheme of the invention is that the high-entropy perovskite integral type catalytic device is applied to catalytic combustion purification of methane in ventilation gas of coal mines, 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 integral catalytic device with a three-dimensional ordered macroporous structure for the first time, firstly preparing a metal sol dispersion liquid containing PS microspheres, and then coating the porous ceramic material on a honeycomb (ceramic) substrate, and finally calcining to remove the carbon template to obtain the high-entropy perovskite catalytic device with the three-dimensional ordered macroporous structure. The preparation method is simple and easy for industrial macro preparation, and realizes the simplified one-step preparation of the three-dimensional ordered macroporous structure high-entropy catalyst.
(2) The three-dimensional ordered macroporous structure of the three-dimensional ordered large Kong Gaoshang perovskite monolithic catalytic device prepared by the invention ensures that the catalyst has good mass transfer diffusion performance and catalytic oxidation activity. In addition, the three-dimensional ordered large Kong Gaoshang perovskite integral type catalytic device has higher configuration entropy, and endows the catalyst with severe lattice distortion and abundant defects, so that the catalyst has excellent catalytic combustion activity and stability (good high temperature resistance, moisture resistance and sulfur resistance).
(3) The catalyst has the advantages of low price of the active components, better economy, and great economic and environmental benefits.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are 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 other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a physical image, a scanning electron microscope image, an X-ray diffraction pattern (XRD) and an EDS-Mapping pattern of HEPO of the catalytic device prepared in the embodiment 1, wherein a is the physical image, b is the scanning electron microscope image, c is the X-ray diffraction pattern, and d is the EDS-Mapping pattern;
FIG. 2 is a graph of the combustion performance of the catalytic device of example 2 in catalyzing soot particulate matter;
FIG. 3 is a graph of the catalytic methane combustion performance of the catalytic device prepared in example 3;
FIG. 4 is a graph showing the catalytic propylene combustion performance of the catalytic device prepared in example 4;
FIG. 5 is a macro-scale preparation physical diagram of the catalytic device of example 3;
FIG. 6 is a graph of the thermal stability and moisture resistance of the catalytic device prepared in example 3;
FIG. 7 is a graph showing the catalytic methane combustion performance of the catalytic devices prepared in example 3 and comparative examples 1 and 2;
FIG. 8is the cycling stability of the catalytic device prepared in example 3;
FIG. 9 is a graph of catalytic methane combustion performance for the catalytic device prepared in example 3 and other differently configured entropy catalytic devices.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 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 invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The honeycomb ceramic substrates used in the examples and comparative examples of the present invention had dimensions of 1.4X1.4X1.5 cm, and other dimensions were also able to achieve the technical effects of the present invention.
Example 1
2G of lanthanum nitrate hexahydrate, 0.4g of nickel nitrate hexahydrate, 0.41g of manganese nitrate tetrahydrate, 0.45g of ferric nitrate hexahydrate, 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 action of ultrasound. 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 prepare a mixed metal salt sol. 3mL of PS (polystyrene) microsphere glycol dispersion with the concentration of 10g/L is added into the mixed metal salt sol, and the mixture is stirred for 24 hours to obtain a dispersion. The honeycomb ceramic substrate is placed in the dispersion liquid to be dip-coated for 24 hours, taken out, dried for 12 hours at 60 ℃, and calcined for 10 hours at 900 ℃, so that the three-dimensional ordered large Kong Gaoshang perovskite (3 DOMLa (NiMnFeCoCu) O 3) integral catalytic device (simply called catalytic device, 3 DOMHEPO) is prepared, the catalyst loading amount is 4%, the pore diameter is 0.5-2 mu m, and the porosity is 3%.
The physical diagram, the scanning electron microscope diagram, the X-ray diffraction diagram (XRD) and the EDS-Mapping diagram of HEPO of the catalytic device prepared by the embodiment are shown in the figure 1, wherein a is the physical diagram, b is the scanning electron microscope diagram, c is the X-ray diffraction diagram and d is the EDS-Mapping diagram. From fig. 1, it can be seen that the catalytic device prepared in this example has microscopic morphological features of a three-dimensional ordered macroporous structure. No phase separation occurs in the XRD pattern, further demonstrating successful preparation of High Entropy Perovskite Oxide (HEPO).
Example 2
2.2G of lanthanum nitrate hexahydrate, 0.4g of chromium nitrate hexahydrate, 0.41g of manganese nitrate tetrahydrate, 0.45g of ferric nitrate hexahydrate, 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 ultrasonic action. 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 prepare a mixed metal salt sol. 3mL of PS microsphere glycol dispersion with the concentration of 10g/L is added into the mixed metal salt sol, and the mixture is stirred for 20 hours to obtain the dispersion. The honeycomb ceramic substrate is placed in the dispersion liquid to be dip-coated for 24 hours, taken out, dried at 70 ℃ overnight, and calcined at 800 ℃ for 10 hours, so that the three-dimensional ordered large Kong Gaoshang perovskite monolithic catalytic device 3DOMLa (CrMnFeCuBi) O 3 (catalytic device, 3DOMHEPO for short), the catalyst loading amount is 10%, the pore diameter is 0.5-2 mu m, and the porosity is 3%.
The catalytic device prepared in the embodiment is used for evaluating and verifying the catalytic combustion performance of the diesel vehicle tail gas soot particles, and the evaluation method is as follows:
The catalyst sample boot catalytic oxidation activity test was performed in an atmospheric fixed bed microreactor. The reactor is made of quartz tube, the inner diameter is 6.4mm, the temperature raising program and the temperature raising rate are automatically controlled by setting the program, the temperature raising program is tested and controlled to be room temperature-200 ℃, the residence time is 30min, 200-700 ℃, the temperature raising rate is 2 ℃ per min, and finally the temperature is kept at 700 ℃ for 30min. The method comprises the steps of preparing a certain amount of suspension liquid by dissolving a certain amount of boot in glycol solution, uniformly dripping the certain amount of suspension liquid on a sample to be tested by using a pipette, drying at 200 ℃, simulating a loose contact mode, and keeping the mass ratio of the catalyst to the boot at 10/1. Subsequently, the sample coated with the loaded boot is placed in a constant temperature area of the reaction tube by using a quartz cotton liner. The reaction gas composition (volume fraction) was 10% O 2,90％N2, and the total gas flow was 50mL/min.
The gas content after the reaction is analyzed on line by using a Fu Li GC-9790 type gas chromatograph, the FID is a detector, the high-purity nitrogen is used as carrier gas, the column furnace temperature is 90 ℃, the detector temperature 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. The catalytic properties were evaluated with T10 and T50, respectively, i.e. corresponding to temperatures at which the boot conversion is 10% and 50%, respectively. The conversion rate of the boot is calculated by dividing the area of the boot converted into CO x peak corresponding to a certain temperature before the certain temperature by the sum of the areas of the boot converted into CO x peak in the whole reaction process.
The test results are shown in fig. 2, wherein T 90 represents the temperature required by the boot conversion rate reaching 90%, and as can be seen from fig. 2, the catalytic device prepared in example 2 shows better boot catalytic combustion activity, is completely oxidized at 550 degrees Csoot, and the catalyst is 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 hexahydrate, 0.41g of manganese nitrate tetrahydrate, 0.45g of ferric nitrate hexahydrate, 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 ultrasonic action. 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 prepare a mixed metal salt sol. 10mL of PS microsphere glycol dispersion with the concentration of 10g/L is added into the mixed metal salt sol and stirred for 1 hour to obtain the dispersion. And (3) putting the honeycomb ceramic substrate into the dispersion liquid, dip-coating for 1 hour, taking out, drying at 80 ℃ overnight, and calcining at 900 ℃ for 20 hours to finally prepare the three-dimensional ordered large Kong Gaoshang perovskite monolithic catalytic device 3DOM (LaCaSrKBi) (CrMnFeCoNi) O 3 (catalytic device for short, 3 DOMHEPO) which comprises 10 elements, wherein the catalyst loading is 10%, the pore diameter is 0.5-2 mu m, 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 methane, and the evaluation method is as follows:
the catalytic combustion activity of CH 4 was evaluated using a quartz tube simulated fixed bed reactor. The catalyst sample to be tested was packed in the middle of a quartz tube. And (3) loading the quartz tube into a tube furnace, connecting a gas circuit, detecting leakage, setting a heating program, namely heating from 25 ℃ to 250 ℃, preserving heat for 25min, heating to 300 ℃ at a heating speed of 10 ℃ per min, preserving heat for 25min, and respectively passing through the temperature range of 350-750 ℃ at the same heating speed and the same heat preserving time. Air was simulated over the catalyst at a total gas flow rate of 50mL/min, and 1% CH 4、5％O2 and 94% N 2 were introduced. The tail gas components of the catalytic reaction were monitored online in real time by gas chromatography (GC-9790). The instrumentation set up for the GC was N 2 for the carrier gas, using a hydrogen Flame Ionization Detector (FID), column oven temperature 70 ℃. The calculation formula for the conversion of CH 4 is:
wherein X methane in the formula represents the conversion rate of methane, F methane,in represents the inlet concentration of methane, F methane,out represents the outlet concentration of methane after catalytic oxidation, and F methane,in-Fmethane,out represents the concentration of methane converted during catalytic oxidation. T 90 represents the temperature at which the methane conversion is 90%.
The test results are shown in FIG. 3, in which round1 indicates the 1 st round of catalyst use, round2 indicates the 2 nd round of catalyst use, and round3 indicates the 3 rd round of catalyst use. It can be seen from fig. 3 that the catalytic device prepared in example 3 exhibited a better 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 50 hours of use.
Fig. 6 shows the thermal stability and moisture resistance of the catalytic device prepared in example 3. It can be seen from fig. 6 that the high entropy perovskite prepared in example 3 can maintain good catalytic activity both through thermal aging in an air atmosphere at 800 ℃ and 10% humidity, and the conversion rate of the catalyst for catalytic CH 4 oxidation to CO 2 is not substantially reduced at 450 ℃.
Fig. 8 shows the cycle stability of the catalytic device prepared in example 3, and fig. 8 shows that the catalytic combustion activity of the three-dimensional ordered large Kong Gaoshang perovskite catalytic device (3 DOMHEPO) prepared in example 3 is not reduced after the catalytic device is recycled for 20 times, and the catalytic combustion activity of the catalytic CH 4 is oxidized to CO 2.
Example 4
1G of lanthanum nitrate hexahydrate, 0.4g of chromium nitrate hexahydrate, 0.41g of manganese nitrate tetrahydrate, 0.45g of ferric nitrate hexahydrate, 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 were added, and stirred on a magnetic stirrer for 10 minutes to prepare a mixed metal salt sol. 20ml of PS microsphere glycol dispersion with the concentration of 10g/L is added into the mixed metal salt sol and stirred for 24 hours to obtain the dispersion. And (3) putting the honeycomb ceramic substrate into the dispersion liquid, dip-coating for 10 hours, taking out, drying at 100 ℃ overnight, and calcining at 760 ℃ for 10 hours to finally prepare the three-dimensional ordered large Kong Gaoshang perovskite monolithic catalytic device 3DOMLa (CrMnFeBiCu) O 3 (catalytic device, 3DOMHEPO for short), wherein the catalyst loading is 10%, the pore diameter is 0.5-2 mu m, and the porosity is 4%.
The catalytic device prepared in this example was evaluated for the catalytic combustion performance of VOCs (propylene) by the method of evaluating the catalytic oxidation activity of C 3H8 of the catalyst sample using a quartz tube simulated fixed bed reactor. The catalyst sample to be tested was packed in the middle of a quartz tube and the temperature programmed from 200 ℃ to 700 ℃ (5 ℃ per min; 50 ℃ per stage intervals) and each temperature stage was maintained for 30 minutes. The reaction gas had a composition of 3000ppm C 3H8、12％O2 and N 2 balance, a total flow of 50mL/min and a corresponding mass space velocity of about 37500mLg -1h-1. The tail gas components of the catalytic reaction are monitored on line in real time by gas chromatography (GC-9790 type) of Taizhou Fu Liang Co, N 2 is carrier gas. The apparatus set-up conditions for GC-9790 were N 2 for carrier gas, 90℃for column furnace temperature, 150℃for detection, 200℃for sample injection, and the relative content shown by chromatography was used to represent the propane concentration. Wherein, the calculation formula of C 3H8 conversion is:
Wherein X Propylene in the formula represents the conversion rate of propylene, F Propylene ,in represents the inlet concentration of propylene, F Propylene ,out represents the outlet concentration of propylene after catalytic oxidation, and F Propylene ,in-F Propylene ,out represents the concentration of propylene converted during 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 a good catalytic combustion activity of propylene, and the 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
The preparation method of the La (Mn 0.2Fe0.2Ni0.2Cu0.2Co0.2)O3 @PAC monolithic catalyst comprises the following steps:
1mmol of citric acid is dissolved in 5mL of absolute ethyl alcohol, stirred until the citric acid is completely dissolved, then 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 are respectively weighed, added into the solutions, stirred until the solution is clear, and then stirred for 0.5h continuously, so as to obtain a precursor solution. And (3) transferring 5mL of precursor solution by a transfer gun, dripping the precursor solution on a substrate material, standing for 0.5h at room temperature, drying for 2h at 80 ℃ in a blast drying oven, and calcining for 3h at 600 ℃ in a muffle furnace to obtain the high-entropy perovskite monolithic catalyst La (Mn 0.2Fe0.2Ni0.2Cu0.2Co0.2)O3 @PAC) with the active component loading capacity of 0.6%.
Comparative example 2
The preparation method of the La (Mn 0.2Fe0.2Ni0.2Cu0.2Co0.2)O3 @PAC three-dimensional ordered macroporous monolithic catalyst comprises the following steps:
1mmol of citric acid is dissolved in 5mL of absolute ethyl alcohol, stirred until the citric acid is completely dissolved, then 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 are respectively added into the solutions, stirring is continued for 0.5h after the solution is clarified, a precursor solution is obtained, 20mL of PS microsphere glycol dispersion with the concentration of 10g/L is added into the precursor solution, and stirring is carried out for 24h, so that a dispersion is obtained. And (3) transferring 5mL of the dispersion liquid by a liquid transferring gun, dripping the dispersion liquid on a base material, standing for 0.5h at room temperature, drying for 2h at 80 ℃ in a blast drying oven, and calcining for 3h at 600 ℃ in a muffle furnace to obtain the three-dimensional ordered large Kong Gaoshang perovskite monolithic catalyst 3DOM La (Mn 0.2Fe0.2Ni0.2Cu0.2Co0.2)O3 @PAC) with the active component loading amount of 0.6%.
FIG. 5 is a macro-scale preparation physical diagram of the catalytic device of example 3;
fig. 7 is a graph showing the catalytic methane combustion performance of the catalytic devices prepared in example 3 and comparative examples 1 and 2, and as can be seen from fig. 7, the catalytic device prepared in example 3 has high catalytic combustion activity, the catalytic methane combustion T90 is 500 ℃, the catalytic device in comparative example 1 has catalytic methane combustion T90 is 700 ℃, and the catalytic device in comparative example 2 has catalytic methane combustion T90 is about 600 ℃. The three-dimensional ordered macroporous structure of the high-entropy catalytic device has remarkable promotion effect on catalytic activity, and the large configuration entropy of the multiple elements selected by the high-entropy catalytic device has promotion effect on the activity of the catalyst. The three-dimensional ordered macroporous structure and the high-entropy structure act together to obviously reduce the catalytic conversion temperature T90 of the catalyst (700 ℃ to 500 ℃).
Fig. 9 is a graph of the catalytic combustion performance of the catalytic device prepared in example 3 and other entropy catalytic devices of different configurations, and it can be seen from fig. 9 that the high entropy catalytic device according to the present invention exhibits better catalytic combustion activity than conventional low-entropy and medium-entropy perovskites. As the configuration entropy increases, the T90 conversion temperature of the catalyst drops significantly (700 ℃ to 500 ℃).
In the process of catalytic oxidation of motor vehicle exhaust (CO, NO, CH x and boot), the catalytic activity of the catalyst can be influenced by both the contact efficiency of reactants and the catalyst and the intrinsic activity of active sites of the catalyst. The mass transfer and diffusion processes of the reactants occurring at the catalyst surface can have a significant impact on the performance of the catalyst. According to the invention, 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 the laboratory stage, and a mild and feasible preparation method which is easy to scale up is lacked. The invention provides a mild, feasible and easily-amplified preparation method (shown in figure 5), which is used for synthesizing an integral high-entropy perovskite catalytic device with a three-dimensional ordered macroporous microstructure, and is applied to the field of environmental thermocatalysis and has a good catalytic oxidation effect.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (4)
1. The high-entropy perovskite monolithic catalytic device is characterized by comprising a substrate and high-entropy perovskite oxide, wherein the high-entropy perovskite oxide is supported 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 element A is one or more of Ca, K, la, sr, bi, gd, nd, sm, Y, element B is one or more of Cr, mn, fe, co, ni, cu, ti, al, and at least one of element A and element B consists of five or more elements with equal molar ratio;
the preparation method of the high-entropy perovskite monolithic catalytic device comprises the following steps:
Adding salt containing element A and salt containing element B into water to dissolve, then adding organic acid and organic solvent to obtain mixed metal salt sol, adding polystyrene microsphere dispersion liquid into the mixed metal salt sol to obtain mixed dispersion liquid;
the loading amount of the high-entropy perovskite oxide is 1-20wt%;
The matrix is a ceramic matrix or a metal alloy matrix with a honeycomb structure, the pore diameter of the three-dimensional ordered macroporous structure is 0.5-2 mu m, and the porosity is 1-20%;
The salt containing the element A is nitrate of the element A, the salt containing the element B is nitrate of the element B, the organic acid is oxalic acid, citric acid or fruit acid, the organic solvent is glycol, and the polystyrene microsphere dispersion liquid is polystyrene microsphere glycol dispersion liquid;
the concentration of the polystyrene microsphere dispersion liquid is 10g/L, and 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 microsphere is 5:1;
The time of the impregnation is 24 hours, the drying is particularly 50 ℃ for 20 hours, and the calcining is particularly 800 ℃ for 48 hours.
2. The use of a high entropy perovskite monolithic catalytic device as defined in claim 1 in the manufacture of a diesel vehicle exhaust particulate trap.
3. The use of the high entropy perovskite monolithic catalytic device according to claim 1 in catalytic combustion purification of VOCs in the coal industry, wherein the catalytic combustion purification temperature is 150-400 ℃.
4. Use of a high entropy perovskite monolithic catalytic device according to claim 1 in catalytic combustion purification of coal mine ventilation gas methane, wherein the catalytic combustion purification is at a temperature of 350-600 ℃.
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