CN113860911B - High-entropy ferrite porous ceramic material and preparation method and application thereof - Google Patents
High-entropy ferrite porous ceramic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-entropy ferrite porous ceramic material and a preparation method and application thereof, belonging to the field of inorganic functional materials. The high-entropy ferrite porous ceramic material has the chemical composition of (Mg) 0.4‑x Co x Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Wherein x has a value in the range of 0<x is less than or equal to 0.2. The preparation method comprises the following steps: dissolving glycine, magnesium nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, copper nitrate and ferric nitrate in water to obtain a mixed solution; adjusting the pH value of the obtained mixed solution, and heating the mixed solution until the solution generates a combustion reaction to obtain precursor powder; and carrying out heat treatment, molding and sintering on the obtained precursor powder to obtain the high-entropy ferrite porous ceramic material. The high-entropy ferrite porous ceramic material disclosed by the invention integrates the advantages of high entropy effect and foam structure synergistic effect, has self-supporting capability and high specific surface area, is convenient to transport, store and recycle, and has a good application prospect.
Description
Technical Field
The invention belongs to the field of inorganic functional materials, and particularly relates to a high-entropy ferrite porous ceramic material, and a preparation method and application thereof.
Background
The waste liquid, automobile exhaust and industrial waste gas discharged in the current industrial production bring serious harm to the living environment of human beings, and pollutants in the waste liquid and the waste gas are mainly various organic matters or CO and nitrogen oxides, have complex components and extremely high difficulty in direct purification treatment. Heterogeneous catalytic degradation technology is a typical strategy for economically efficient removal of pollutants.
Spinel type ferrite (structural general formula AFe) 2 O 4 A ═ Fe, Cu, Ni, Co, Mn, Zn, and the like) has magnetism, and microstructures such as varied oxygen defect vacancies in the crystal lattice, combinations of valence states of various metal ions, and easily excited energy bands cause varied micro-interface characteristics, so that they have attracted attention as heterogeneous catalysts. However, conventional spinel ferrites (AFe) 2 O 4 ) In the actual wastewater treatment application of the heterogeneous catalyst activated persulfate for degrading the emerging organic pollutants, the problems that nano powder particles are easy to run off when effluent is discharged, the recovery rate is low, nano magnetic particles are easy to agglomerate, and the contact area between active sites and target pollutants is reduced, so that the activation degradation efficiency is not high generally exist.
In addition, the method is applied to AFe in strong acid or strong alkaline wastewater environment 2 O 4 Heterogeneous catalysts are weak in stability, surface dissolution and ion leaching are easy to occur, and the risk of secondary metal ion pollution is faced. In recent years, the appearance of high-entropy ceramics is a new breakthrough on the basic problem of material science, namely the relationship between the composition, structure and performance of materials. The traditional ferrite material research work always has a main crystal phase which is modified by doping small amount of other metal ions or oxides, and the research object of the high-entropy spinel ferrite is to proceed to the inner central region of a multi-component polyhedronThe design limitation of simple component components is broken through, and a wider thought is provided for the research and development of a new material system and the optimization of key performance.
Chinese patent application CN113332988A discloses a porous magnetic conductive copper-doped copper-zinc ferrite catalyst, a preparation method and application thereof, wherein the chemical formula of the catalyst is Cu x -Cu (0.5-x) Zn 0.5 Fe 2 O (4-x) And the catalyst is used in combination with ozone to treat antibiotic wastewater. However, in this technique, spinel type ferrite (structural formula AFe) 2 O 4 ) The component number on the A lattice site is less than 5, the mutual synergistic catalytic action of multiple components is weaker, and meanwhile, the catalyst is still powdery particles, so that the loss during effluent discharge is difficult to avoid, and the recovery rate is low.
Chinese patent application CN113045304A discloses a mixed spinel structure ferrite wave-absorbing material and a preparation method thereof, and the molecular formula is Co 1-x Ni x Fe 2 O 4 The result shows that the material has a good microwave absorption effect in a 2-18 GHz microwave band, but the material is still powdery and has no self-supporting capability, and the component types of the A lattice site are less than 5.
In conclusion, the prior art still lacks a ferrite multifunctional material which has a certain macroscopic size, is beneficial to portable transportation, storage and recycling, has self-supporting capability and integrates a high-entropy effect and a foam structure.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method and application of a high-entropy ferrite porous ceramic material, wherein the high-entropy ferrite porous ceramic material integrates the advantages of high entropy effect and foam structure synergistic effect, has self-supporting capacity and high specific surface area, is convenient to transport, store and recycle, and has good application prospect in the fields of treating organic pollutants in wastewater, wave-absorbing materials and purifying and treating automobile exhaust by using a heterogeneous activated persulfate oxidation technology.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on the one handThe invention provides a high-entropy ferrite porous ceramic material with a chemical formula of (Mg) 0.4- x Co x Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Wherein x has a value in the range of 0<x≤0.2。
Preferably (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 。
Preferably, the high-entropy ferrite porous ceramic material is mainly provided with open pores, the total porosity is 70-95%, and the grain size is 0.2-1.2 μm.
On the other hand, the invention provides a preparation method of the high-entropy ferrite porous ceramic material, which comprises the following steps:
s1, dissolving glycine, magnesium nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, copper nitrate and ferric nitrate in water to obtain a mixed solution;
the molar ratio of the magnesium nitrate, the cobalt nitrate, the nickel nitrate, the zinc nitrate, the copper nitrate and the ferric nitrate is (0.4-x) x is 0.2:0.2:0.2:2, and x is more than 0 and less than or equal to 0.2; preferably 0.2:0.2:0.2:0.2:0.2: 2.
S2, adjusting the pH value of the mixed solution obtained in the step S1, and heating the mixed solution until the solution generates a combustion reaction to obtain precursor powder;
s3, carrying out heat treatment, molding and sintering on the precursor powder obtained in the step S2 to obtain the high-entropy ferrite porous ceramic material.
Wherein the content of the first and second substances,
in step S1, the water may be distilled water, purified water, desalted water, tap water, drinking water, ultrapure water, or the like, and preferably distilled water is used.
In step S1, glycine may be added before or after the addition of magnesium nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, copper nitrate, and iron nitrate.
Preferably, in step S1, the molar ratio of nitrate ions to glycine in the mixed solution is 2-3: 1.
preferably, in step S2, the pH value is 2-6.
In step S2, the pH adjustment can be performed by using pH adjusting agent commonly used in the art, and the pH adjusting agent includes, but is not limited to, concentrated ammonia water, triethylamine, etc., preferably, the pH adjustment is performed by using concentrated ammonia water, and more preferably, the concentrated ammonia water is 25-28 wt% concentrated ammonia water.
Preferably, in step S2, the heating is performed in a heat-resistant vessel, and more preferably a heat-resistant vessel having a large evaporation surface, such as a quartz crucible or the like. Heating first causes the water content of the solution to evaporate and eventually a combustion reaction occurs. Preferably, the power of the heating source for heating is 2.0-6.0KW, and more preferably 2.5 KW.
Preferably, the combustion reaction time is 20-30 min.
Preferably, in step S3, the heat treatment conditions are: keeping the temperature at 950 ℃ and 1300 ℃ for 2-3 h.
Preferably, the method further comprises the following steps after the heat treatment: and respectively processing the powder after heat treatment by a sieve of 80 meshes and a sieve of 200 meshes, wherein the grain diameter of secondary particles of the powder is 15-25 mu m.
Preferably, in step S3, the molding manner is ball milling foaming, more preferably wet ball milling foaming, and still more preferably, the wet ball milling foaming process conditions are as follows: the medium is distilled water, the solid content of the slurry is 20-35vol%, the dispersant is a copolymer of isobutene and maleic anhydride, the cationic surfactant is dodecyl trimethyl ammonium chloride, and the mixture is ball-milled for 1-3h at 250-350 r/min. The amounts of the distilled water, the dispersant and the cationic surfactant used in the present invention are those known in the art to be able to perform ball milling foaming smoothly, and are not particularly limited. For example, the dispersant may be used in an amount of 0.1 to 20 wt% and the cationic surfactant may be used in an amount of 0.1 to 20 wt% based on the mass of the powder.
Preferably, a drying step is further included after the molding. Further preferably, the drying is: the foam slurry after ball milling foaming is preferably poured into a mold and dried at room temperature. The mold is not particularly limited and can be a plastic mold, a paper box, a metal mold and the like; the diameter and shape are not particularly limited, and it is sufficient to prepare a green body in accordance with the diameter and shape well known in the art, for example, a sphere, a cylinder, a cube, a cuboid, a pyramid, and various irregular or special-shaped polygons.
Preferably, in step S3, the sintering is staged, constant temperature and pressure sintering.
Further preferably, the staged incubation process comprises: the first stage is as follows: the calcination temperature is 500-600 ℃, and the heat preservation is carried out for 1-3 h; and a second stage: the calcining temperature is 1100-1300 ℃, and the heat preservation time is 1-4 h.
Still further preferably, the staged incubation process comprises: the first stage is as follows: the calcination temperature is 550 ℃, and the heat preservation is carried out for 2 hours; and a second stage: the calcination temperature is 1200 ℃ and 1250 ℃, and the heat preservation time is 2 h.
Further preferably, the temperature rise rate of the first stage is 2-3 ℃/min, and most preferably 2 ℃/min; the temperature rise rate of the second stage is 1.5-2 ℃/min, most preferably 1.5 ℃/min.
The method is used for calcining in a mode of two-stage heat preservation and gradually reduced temperature rise rate of each stage, is beneficial to prolonging the heating time of a sample, promotes the internal temperature to be uniformly distributed, and is easier to obtain a single-phase high-entropy ferrite product during heat preservation, so that the prepared porous ceramic skeleton has no cracks, pure phase, high specific strength and amorphous phase, and meets the application requirements of the fields of organic dye degradation by activated persulfate, automobile exhaust purification treatment and wave-absorbing materials on spinel type ferrite materials.
Finally, the invention provides the application of the high-entropy ferrite porous ceramic material in the treatment of organic pollutants in wastewater and wave-absorbing materials by a heterogeneous activated persulfate oxidation technology and the application of the high-entropy ferrite porous ceramic material as a catalyst carrier in the treatment of automobile exhaust.
The invention has the beneficial effects that:
(1) the invention provides a high-entropy ferrite porous ceramic material, which integrates the advantages of high-entropy effect and foam structure synergistic effect, has self-supporting capacity and high specific surface area, and is convenient to transport, store and recycle;
(2) the high-entropy ferrite porous ceramic material provided by the invention is cheap in preparation raw materials, convenient and fast in process regulation, beneficial to popularization, stable in phase and controllable in pore structure and chemical components;
(3) the preparation method of the high-entropy ferrite porous ceramic material provided by the invention has the characteristics of simple and convenient process, good controllability, relatively simple sintering conditions, easiness in operation and production and the like;
(4) the high-entropy ferrite porous ceramic provided by the invention is a three-dimensional porous high-entropy foam material, integrates the advantages of a high-entropy effect, a component synergistic effect and a 3D porous structure, has a three-dimensional self-supporting structure and a large specific surface area, has rich active centers, and provides a new opportunity for developing a heterogeneous catalysis system with high catalytic activity and high stability;
(5) (Mg) provided by the invention 0.4-x Co x Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The high-entropy porous material has a great application value in the fields of organic dye degradation by activated persulfate, automobile exhaust purification treatment and wave-absorbing materials, and is a multifunctional inorganic material with excellent catalytic performance and wave-absorbing property.
Drawings
FIG. 1 is an XRD pattern of a product after heat treatment of precursor powder at 1000 ℃ for 3 hours.
FIG. 2 shows high entropy (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 SEM image of porous ceramic skeleton part.
FIG. 3 shows high entropy (Mg) 0.3 Co 0.1 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 SEM image of porous ceramic.
FIG. 4 shows high entropy (Mg) at different initial pH values 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Kinetics process diagram of degradation of tetracycline hydrochloride (TCH) by activated Peroxodisulfate (PDS).
FIG. 5 shows high entropy (Mg) at different initial pH values 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 A kinetic process diagram of porous ceramic activated Peroxodisulfate (PDS) degrading rhodamine B (RhB).
FIG. 6 is high entropy (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Porous ceramics, high entropy (Mg) 0.3 Co 0.1 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Porous ceramic, single component ZnFe 2 O 4 Porous ceramic, single component CoFe 2 O 4 Porous ceramic, four-component (Co) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 And four components (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Comparative analysis of the degradation behaviour of porous ceramic activated Peroxodisulfate (PDS) to methylene blue.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. The following is merely an exemplary illustration of the scope of the invention as claimed, and various changes and modifications of the invention of the present application may be made by those skilled in the art based on the disclosure, which also fall within the scope of the invention as claimed. The term "about" means within 10% of a certain value, e.g. about 20 microns, i.e. 20 ± 2 microns.
The present invention will be further described below by way of specific examples. The various chemicals used in the examples of the present invention were obtained by conventional commercial routes unless otherwise specified.
In the embodiment described below, it is preferred that,
magnesium nitrate was purchased from national pharmaceutical group chemical reagents ltd, having a product number of Shanghai test/80075918 (analytical purity);
cobalt nitrate was purchased from national pharmaceutical group chemical reagents ltd, with a product number of Shanghai test/80141814 (analytical purity);
the nickel nitrate is purchased from national pharmaceutical group chemical reagent limited, and the product number is Shanghai test/10014360 (analytical purity);
zinc nitrate was purchased from national pharmaceutical group chemical reagent GmbH, having a product number of Shanghai test/80141328 (analytical purity);
copper nitrate was purchased from national pharmaceutical group chemical reagent limited, under the trade designation Hu test/10007916 (analytical purity);
the ferric nitrate is purchased from national pharmaceutical group chemical reagent limited, and the product number is Shanghai test/80072718 (analytical purity);
glycine is purchased from national pharmaceutical group chemical reagent, Inc., and its product number is Shanghai test/62011516 (analytical purity);
ammonia water is purchased from Xiong science corporation, with a concentration of 25-28 wt%;
isobutylene and maleic anhydride copolymer was purchased from Colorado, Japan, model number PIBM # 104;
dodecyl trimethyl ammonium chloride is purchased from chemical reagent of national medicine group Limited, national medicine No. 30199370, and has purity of 98% (Hu test).
Example 1 high entropy (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Preparation of porous ceramic material
According to (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The magnesium nitrate, the cobalt nitrate, the nickel nitrate, the zinc nitrate, the copper nitrate and the ferric nitrate are weighed according to the stoichiometric ratio of (0.4-x): x:0.2:0.2:0.2:2, and x ═ 0.2, and the obtained mixture is mixed with distilled water; fuel glycine was also added according to the chemical equation for a complete combustion reaction, with a molar ratio of nitrate ions to glycine of 2: 1, stirring to completely dissolve the mixture to obtain a mixed solution.
Adjusting the pH value of the mixed solution to 4.1 by ammonia water to obtain a precursor solution, transferring the precursor solution to a quartz crucible, heating the quartz crucible on an electric furnace to evaporate water and finally carrying out combustion reaction to obtain precursor powder.
And placing the obtained precursor powder in a muffle furnace, and preserving heat for 3 hours at 1000 ℃ to carry out powder heat treatment to obtain the high-entropy ferrite powder. FIG. 1 is a high entropy ferrite XRD diffraction pattern of a single spinel type phase synthesized after precursor powder is placed in a muffle furnace and is kept at 1000 ℃ for 3 hours.
The prepared high-entropy ferrite powder is subjected to 80-mesh and 200-mesh treatment to obtain powder with good dispersibility, and the average particle size of secondary particles of the powder is about 20 mu m;
ball milling and foaming: mixing the screened high-entropy ferrite powder with distilled water, carrying out ball milling foaming, controlling the solid content of the slurry to be 32.5 vol%, controlling the adding amount of the isobutylene-maleic anhydride copolymer (PIBM104#) to be 0.3 wt% relative to the mass of the powder, controlling the adding amount of the cationic surfactant to be 0.04 wt% relative to the mass of the powder, controlling the ball milling rotation speed to be 300r/min, and controlling the ball milling time to be 1 h.
Drying and forming: placing the wet foam in a circular plastic mould, and naturally drying at room temperature for 36 hours to obtain a cylindrical blank;
and (3) staged calcination: putting the cylindrical blank into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2h, heating to 1200 ℃ at the speed of 1.5 ℃/min, preserving heat for 2h, and cooling with the furnace to obtain high entropy (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 A porous ceramic. FIG. 2 shows the high entropy (Mg) produced in this example 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 And (5) testing results of the porous ceramic by SEM.
Example 2 high entropy (Mg) 0.3 Co 0.1 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Preparation of porous ceramic material
According to (Mg) 0.3 Co 0.1 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The magnesium nitrate, the cobalt nitrate, the nickel nitrate, the zinc nitrate, the copper nitrate and the ferric nitrate are weighed according to the stoichiometric ratio of (0.4-x): x:0.2:0.2:0.2:2, and x ═ 0.1, and the obtained mixture is mixed with distilled water; fuel glycine was also added according to the chemical equation for a complete combustion reaction, with a molar ratio of nitrate ions to glycine of 3: 1, stirring to completely dissolve the mixture to obtain a mixed solution.
Adjusting the pH value of the mixed solution to 5.2 by using ammonia water to obtain a precursor solution, transferring the precursor solution to a quartz crucible, heating the quartz crucible on an electric furnace to evaporate water and finally carrying out combustion reaction to obtain precursor powder.
And placing the obtained precursor powder in a muffle furnace, and carrying out heat treatment on the powder for 3 hours at 950 ℃ to obtain the high-entropy ferrite powder.
The prepared high-entropy ferrite powder is subjected to 80-mesh and 200-mesh treatment to obtain powder with good dispersibility.
Ball-milling and foaming: mixing the screened high-entropy ferrite powder with distilled water, carrying out ball milling foaming, controlling the solid content of the slurry to be 32.5 vol%, controlling the adding amount of the isobutylene-maleic anhydride copolymer (PIBM104#) to be 0.3 wt% relative to the mass of the powder, controlling the adding amount of the cationic surfactant to be 0.04 wt% relative to the mass of the powder, controlling the ball milling rotation speed to be 300r/min, and controlling the ball milling time to be 1 h.
Drying and forming: placing the wet foam in a circular plastic mould, and naturally drying at room temperature for 36 hours to obtain a cylindrical blank;
and (3) staged calcination: putting the cylindrical blank into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2h, heating to 1200 ℃ at the speed of 1.5 ℃/min, preserving heat for 2h, and cooling with the furnace to obtain high entropy (Mg) 0.3 Co 0.1 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 A porous ceramic. FIG. 3 shows the high entropy (Mg) produced in this example 0.3 Co 0.1 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 And (4) testing results of the porous ceramic by SEM.
Comparative example 1 Single component ZnFe 2 O 4 Preparation of porous ceramic material
According to ZnFe 2 O 4 The zinc nitrate and the ferric nitrate are weighed, and the obtained mixture is mixed with distilled water; fuel glycine was also added according to the chemical equation for a complete combustion reaction, with a molar ratio of nitrate ions to glycine of 2: 1, the mixture was stirred to be completely dissolved, and then the pH of the solution was adjusted to 4.3 with aqueous ammonia. Transferring the precursor solution to a quartz crucible, heating the quartz crucible on an electric furnace to evaporate water and finally carrying out combustion reaction, and then placing the obtained precursor powder in a muffle furnace at 10 DEG CKeeping the temperature at 00 ℃ for 3 hours to carry out heat treatment on the powder. The ZnFe produced 2 O 4 The powder is processed by 80 meshes and 200 meshes to obtain powder with better dispersibility; then, mixing the obtained high-entropy ferrite powder with distilled water, carrying out ball milling foaming, controlling the solid content of the slurry to be 32.5 vol%, controlling the adding amount of isobutylene and maleic anhydride copolymer (PIBM104#) to be 0.3 wt% relative to the mass of the powder, controlling the adding amount of Dodecyl Trimethyl Ammonium Chloride (DTAC) as a cationic surfactant to be 0.04 wt% relative to the mass of the powder, controlling the ball milling rotation speed to be 300 revolutions per minute, and controlling the ball milling time to be 1 hour, and pouring wet foam into a circular plastic mold; drying and molding, namely naturally drying the wet foam in the round plastic mold at room temperature for 36 hours; and finally, calcining by stages, namely putting the cylindrical blank into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2h (the first stage), heating to 1200 ℃ at the speed of 1.5 ℃/min, preserving heat for 2h, and cooling along with the furnace to obtain the single component ZnFe 2 O 4 A porous ceramic.
Comparative example 2 monocomponent CoFe 2 O 4 Preparation of porous ceramic material
According to CoFe 2 O 4 The cobalt nitrate and the ferric nitrate are weighed, and the obtained mixture is mixed with distilled water; fuel glycine was also added according to the chemical equation for a complete combustion reaction, with a molar ratio of nitrate ions to glycine of 2: 1, the mixture was stirred to be completely dissolved, and then the pH of the solution was adjusted to 4.3 with aqueous ammonia. Transferring the precursor solution to a quartz crucible, heating on an electric furnace to evaporate water and finally carrying out combustion reaction, and then placing the obtained precursor powder in a muffle furnace to carry out heat treatment on the powder for 3 hours at 1000 ℃. The prepared high-entropy ferrite powder is subjected to 80-mesh and 200-mesh treatment to obtain powder with good dispersibility; then, the resulting CoFe 2 O 4 Mixing the powder with distilled water, performing ball milling foaming, controlling the solid content of the slurry to be 32.5 vol%, controlling the adding amount of the isobutylene and maleic anhydride copolymer (PIBM104#) to be 0.3 wt% relative to the mass of the powder, and controlling the adding amount of the Dodecyl Trimethyl Ammonium Chloride (DTAC) as a cationic surfactant to be 0.04 wt% relative to the mass of the powderPercent, the ball milling rotating speed is 300r/min, the ball milling time is 1 hour, and the wet foam is poured into a round plastic mould; drying and molding, namely naturally drying the wet foam in the round plastic mold at room temperature for 36 hours; and finally, carrying out staged calcination, namely putting the cylindrical blank into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2h (the first stage), heating to 1200 ℃ at the speed of 1.5 ℃/min, preserving heat for 2h, and cooling along with the furnace to obtain the single-component CoFe 2 O 4 A porous ceramic.
Comparative example 3 four-component (Co) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Preparation of porous ceramic material
According to (Co) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The cobalt nitrate, the nickel nitrate, the zinc nitrate, the copper nitrate and the ferric nitrate are weighed according to the stoichiometric ratio (namely 0.4:0.2:0.2:0.2:2, x is 0.4), and the obtained mixture is mixed with distilled water; fuel glycine was also added according to the chemical equation for a complete combustion reaction, with a molar ratio of nitrate ions to glycine of 2.5: 1, stirring to completely dissolve the mixture to obtain a mixed solution. And adjusting the pH value of the mixed solution to 4.7 by using ammonia water to obtain a precursor solution, transferring the precursor solution to a quartz crucible, heating the quartz crucible on an electric furnace to evaporate water, and finally performing combustion reaction to obtain precursor powder. Putting the obtained precursor powder into a muffle furnace, and preserving the heat at 1100 ℃ for 3 hours to carry out powder heat treatment to obtain four-component (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 And (3) powder. The prepared four-component (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The powder is processed by 80 meshes and 200 meshes to obtain the powder with better dispersibility. Sieving four components (Co) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Mixing the powder with distilled water, performing ball milling foaming, controlling the solid content of the slurry to be 32.5 vol%, controlling the adding amount of isobutylene and maleic anhydride copolymer (PIBM104#) to be 0.3 wt% relative to the mass of the powder, and using dodecyl trimethyl ammonium sulfate as a cationic surfactantThe addition amount of methyl ammonium chloride (DTAC) is 0.04 wt% relative to the mass of the powder, the ball milling rotation speed is 300r/min, and the ball milling time is 1 h. Placing the wet foam in a circular plastic mould, and naturally drying at room temperature for 36 hours to obtain a cylindrical blank; then putting the cylindrical blank into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2h, heating to 1250 ℃ at the speed of 1.5 ℃/min, preserving heat for 2h, and cooling with the furnace to obtain four-component (Co) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 A porous ceramic.
Comparative example 4 four Components (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Preparation of porous ceramic material
According to (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The raw materials are mixed according to the stoichiometric ratio of (namely 0.2:0.2:0.2:0.2:2, x is 0), magnesium nitrate, nickel nitrate, zinc nitrate, copper nitrate and ferric nitrate are weighed, and the obtained mixture is mixed with distilled water; fuel glycine was also added according to the chemical equation for a complete combustion reaction, with a molar ratio of nitrate ions to glycine of 2.5: 1, stirring to completely dissolve the mixture to obtain a mixed solution. And adjusting the pH value of the mixed solution to 4.7 by using ammonia water to obtain a precursor solution, transferring the precursor solution to a quartz crucible, heating the quartz crucible on an electric furnace to evaporate water, and finally performing combustion reaction to obtain precursor powder. Putting the obtained precursor powder into a muffle furnace, and preserving the heat at 1100 ℃ for 3 hours to carry out powder heat treatment to obtain four-component (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 And (3) powder. The prepared four-component (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The powder is processed by 80 meshes and 200 meshes to obtain the powder with better dispersibility. Sieving four components (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Mixing the powder with distilled water, performing ball milling foaming, controlling the solid content of the slurry to be 32.5 vol%, controlling the adding amount of isobutylene and maleic anhydride copolymer (PIBM104#) to be 0.3 wt% relative to the mass of the powder, and controlling the cationic surface activityThe addition amount of Dodecyl Trimethyl Ammonium Chloride (DTAC) is 0.04 wt% of the powder mass, the ball milling rotation speed is 300r/min, and the ball milling time is 1 h. Placing the wet foam in a circular plastic mould, and naturally drying at room temperature for 36 hours to obtain a cylindrical blank; then putting the cylindrical blank into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2h, heating to 1250 ℃ at the speed of 1.5 ℃/min, preserving heat for 2h, and cooling with the furnace to obtain four-component (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 A porous ceramic.
Characterization and Performance testing
1) XRD test is carried out on the product of the precursor powder in example 1 after being placed in a muffle furnace and heat-treated at 1000 ℃ for 3 hours, and the result is shown in figure 1; as can be seen from FIG. 1, the diffraction peak of the synthesized powder is located between five single components, which indicates that five elements have good solid solution in the crystal lattice, the formation of compatibility and solid solution between the elements is promoted by the high configuration entropy formed by the equimolar ratio, and no other miscellaneous peak and the second phase appear, which indicates that the high entropy material (Mg) with single phase is successfully synthesized 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 。
2) For the high entropy (Mg) prepared in example 1 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Analyzing the microstructure of the porous ceramic (see figure 2); as can be seen from FIG. 2, high entropy (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The average crystal grain of the porous ceramic is about 0.35 mu m, rich pores are distributed on the skeleton part of the porous ceramic, the pore size has the micro-nano dual-scale characteristic, rich active centers are provided, and most of the pores on the skeleton part of the porous ceramic are in the range of 300-800 nm. High entropy (Mg) for example 2 preparation 0.3 Co 0.1 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Analyzing the micro-morphology of the porous ceramic material (shown in figure 3); from FIG. 3, it can be seen that the entropy (Mg) is high 0.3 Co 0.1 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The porous ceramic has rich pore structures, the pore sizes have the characteristics of micro-nano dual-scale, and rich active centers are obtained.
3) After the precursor powder in example 1 is subjected to heat treatment at 1000 ℃ for 3 hours, high entropy (Mg) of a single phase is prepared 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The powder, the performance of activating persulfate to degrade antibiotics under different initial pH values is tested, and the result is shown in figure 4. The reaction process is as follows: 240mL tetracycline hydrochloride solution (TCH, concentration 50Mg/L) was measured, and then ammonia was used to adjust the initial pH of the solution to a target value, 4mM Peroxodisulfate (PDS) concentration, high entropy (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The powder concentration is 0.5 g/L. The removal rate (Rev (%)) of the simulated target pollutant TCH can be calculated by the following formula:
wherein C is t Representing the concentration of organic contaminants in the filtrate at a certain time; c 0 Represents the concentration of the initial organic contaminant; a. the t Representing the absorbance of the organic pollutant in the filtrate at the maximum absorption wavelength (the characteristic absorption peak of the tetracycline hydrochloride is 359nm) at a certain time; a. the 0 Representing the absorbance at the wavelength of maximum absorption of the initial organic contaminant. From FIG. 3, the pH vs. high entropy (Mg) of the different initial solutions can be seen 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The catalytic activation performance of the powder has a remarkable influence, and the high entropy (Mg) is high under the condition of a slightly acidic initial pH (for example, the pH is 3.077) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The powder has better catalytic activity.
4) For the high entropy (Mg) prepared in example 1 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Porous ceramic materialEvaluating the kinetic process of degrading rhodamine B (RhB) organic pollutants by activated persulfate; the reaction process is as follows: a240 mL volume of rhodamine B solution (RhB, concentration 15Mg/L) is measured, and then the initial pH of the solution is adjusted to a target value by ammonia water, the concentration of Peroxydisulfate (PDS) is 4mM, and the entropy (Mg) is high 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The mass concentration of the porous ceramic is 1.5 g/L. The removal rate (Rev (%)) of the simulated target pollutant TCH can be calculated by the following formula:
wherein C is t Representing the concentration of organic contaminants in the filtrate at a certain time; c 0 Represents the concentration of the initial organic contaminant; a. the t Representing the absorbance of the organic pollutant in the filtrate at the maximum absorption wavelength (the characteristic absorption peak of rhodamine B is 553nm) at a certain time; a. the 0 Representing the absorbance at the wavelength of maximum absorption of the initial organic contaminant. The results are shown in FIG. 5, from FIG. 5, it can be seen that the pH of the different initial solutions versus the high entropy (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The property of porous ceramic activated PDS for degrading rhodamine B has a remarkable influence, and the high entropy (Mg) is high under the condition of a slightly acidic initial pH (for example, the pH is 3.022) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The porous ceramic has good catalytic activity, the degradation rate of rhodamine B can reach 66.7% after reaction for 90 minutes, and the fact that the three-dimensional porous high-entropy foam-like ferrite has rich active sites is fully demonstrated.
5) High-entropy ferrite porous ceramics and single component ZnFe prepared respectively for example 1, example 2 and comparative examples 1, 2, 3 and 4 2 O 4 Porous ceramic, single component CoFe 2 O 4 Porous ceramic, four-component (Co) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 And four components (Mg) 0.4 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 And carrying out catalytic activity comparison analysis on the porous ceramic, and selecting activated peroxydisulfate to degrade methylene blue organic dye. The reaction process is as follows: a240 mL volume of methylene blue solution (MB, at a concentration of 15mg/L), a Peroxodisulfate (PDS) concentration of 4mM, and a mass concentration of 1.5g/L for the five types of porous ceramics were measured. The removal rate (Rev (%)) of the simulated target contaminant Methylene Blue (MB) can be calculated by the following formula:
wherein C t Representing the concentration of organic contaminants in the filtrate at a certain time; c 0 Represents the concentration of the initial organic contaminant; a. the t Represents the absorbance of the filtrate at the maximum absorption wavelength (the characteristic absorption peak of methylene blue is 664nm) of the organic pollutants at a certain time; a. the 0 Representing the absorbance at the wavelength of maximum absorption of the initial organic contaminant. As a result, as shown in FIG. 6, it can be seen from FIG. 6 that the entropy (Mg) is high 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 Porous ceramics and high entropy (Mg) 0.3 Co 0.1 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 The porous ceramic has better performance of activating PDS to degrade methylene blue.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (15)
1. A high-entropy ferrite porous ceramic material is characterized in that the chemical formula is (Mg) 0.4-x Co x Ni 0.2 Zn 0.2 Cu 0.2 ）Fe 2 O 4 Wherein x has a value in the range of 0<x≤0.2。
2. A high entropy ferrite porous ceramic material as claimed in claim 1, characterized in thatHas the chemical formula of (Mg) 0.2 Co 0.2 Ni 0.2 Zn 0.2 Cu 0.2 )Fe 2 O 4 。
3. A high entropy ferrite porous ceramic material according to claim 1, characterized in that the total porosity is 70 to 95% with an open pore as a main component, and the grain size is 0.2 to 1.2 μm.
4. A method for preparing a high entropy ferrite porous ceramic material according to any one of claims 1 to 3, comprising the steps of:
s1, dissolving glycine, magnesium nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, copper nitrate and ferric nitrate in water to obtain a mixed solution;
s2, adjusting the pH value of the mixed solution obtained in the step S1, and heating the mixed solution until the solution generates a combustion reaction to obtain precursor powder;
s3, carrying out heat treatment, molding and sintering on the precursor powder obtained in the step S2 to obtain the high-entropy ferrite porous ceramic material.
5. The production method according to claim 4, wherein in step S1, the molar ratio of nitrate ions to glycine in the mixed solution is 2-3: 1.
6. the method according to claim 4, wherein in step S2, the pH is 2-6, and the pH is adjusted by using concentrated ammonia water; the heating is carried out in a heat-resistant vessel; the power of the heating source for heating is 2.0-6.0 KW.
7. The production method according to claim 6, wherein the concentrated aqueous ammonia is 25 to 28 wt% concentrated aqueous ammonia; the heating is carried out in a ovenware having a large evaporation surface; the heating source power of the heating is 2.5 KW.
8. The production method according to claim 4, wherein in step S3, the heat treatment conditions are: keeping the temperature at 950 ℃ and 1300 ℃ for 2-3 h; the method also comprises the following steps after heat treatment: respectively processing the powder after heat treatment by a sieve of 80 meshes and a sieve of 200 meshes, wherein the grain diameter of secondary particles of the powder is 15-25 mu m; the molding mode is ball milling foaming; and a drying step is also included after the forming.
9. The preparation method according to claim 8, wherein the ball milling foaming is wet ball milling foaming; the drying step is as follows: pouring the foam slurry after ball milling foaming into a mould, and drying at room temperature.
10. The preparation method of claim 9, wherein the wet ball milling foaming process conditions are as follows: the medium is distilled water, the solid content of the slurry is 20-35vol%, the dispersant is a copolymer of isobutene and maleic anhydride, the cationic surfactant is dodecyl trimethyl ammonium chloride, and the mixture is ball-milled for 1-3h at 250-350 r/min.
11. The method according to claim 4, wherein in step S3, the sintering is a staged sintering under constant temperature and pressure.
12. The method of claim 11, wherein the staging comprises: the first stage is as follows: the calcination temperature is 500-600 ℃, and the heat preservation is carried out for 1-3 h; and a second stage: the calcination temperature is 1100-1300 ℃, and the heat preservation time is 1-4 h; the temperature rise rate of the first stage is 2-3 ℃/min, and the temperature rise rate of the second stage is 1.5-2 ℃/min.
13. The method of claim 12, wherein the staging comprises: the first stage is as follows: the calcination temperature is 550 ℃, and the heat preservation is carried out for 2 hours; and a second stage: the calcination temperature is 1200 ℃ and 1250 ℃, and the heat preservation time is 2 h.
14. The production method according to claim 12, wherein the temperature rise rate of the first stage is 2 ℃/min; the temperature rise rate in the second stage is 1.5 ℃/min.
15. Use of the high entropy ferrite porous ceramic material according to any one of claims 1-3 or prepared by the preparation method according to any one of claims 4-14 in the treatment of organic pollutants in waste water by heterogeneous activated persulfate oxidation technology, as a wave absorbing material and as a catalyst carrier in the treatment of automobile exhaust.
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