CN111871410A - Magnetic heat-pyroelectric composite material and preparation method and application thereof - Google Patents
Magnetic heat-pyroelectric composite material and preparation method and application thereof Download PDFInfo
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- CN111871410A CN111871410A CN202010802009.XA CN202010802009A CN111871410A CN 111871410 A CN111871410 A CN 111871410A CN 202010802009 A CN202010802009 A CN 202010802009A CN 111871410 A CN111871410 A CN 111871410A
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- composite material
- magnetocaloric
- pyroelectric
- powder
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 239000011572 manganese Substances 0.000 description 3
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a magnetocaloric-pyroelectric composite material and a preparation method and application thereof, belonging to the technical field of sewage treatment. The magnetocaloric-pyroelectric composite material is obtained by adopting a sol-gel method, a hydrothermal method and a microwave sintering method for a magnetocaloric material and a pyroelectric material. The magnetocaloric-pyroelectric composite material obtained by the invention has good stability, and the prepared material contains the magnetocaloric material and can be recycled by using a magnet, so that the loss of a powder sample is small, the powder sample can be repeatedly used for many times, and the recycling rate is high. The magnetocaloric-pyroelectric composite material can be used in organic pollutant degradation applications.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a magnetocaloric-pyroelectric composite material, and a preparation method and application thereof.
Background
In the industrial production process, a large part of dye is lost along with sewage discharge every year, the dye has complex components, difficult decolorization, high organic matter content and good stability in water, has biotoxicity and carcinogenicity, and is recognized as difficultly-degradable sewage which is harmful to the environment and human health if not treated, so that a method for efficiently degrading organic pollutants in sewage is found and important.
The existing method for effectively degrading organic pollutants in sewage comprises a physical method, a chemical method, a biological method and the like, wherein the physical method has small investment and simple and easy operation, but does not degrade the organic pollutants radically, and is more suitable for treating low-concentration dye sewage; the chemical method has higher investment cost and is easy to cause secondary pollution; the biodegradation method has low cost and simple operation, but has higher requirements on environment, such as pH value, temperature and the like of sewage, so the actual degradation effect is not ideal, and the limitations promote the development of advanced oxidation process.
The advanced oxidation technology developed at present includes semiconductor photocatalysis technology, mechanical catalysis technology, thermal catalysis technology and the like, and the common feature of the advanced oxidation technology for effectively degrading organic matters is that active free radicals with strong oxidizing property, such as hydroxyl free radicals, superoxide free radicals and the like, can be generated, and the active free radicals can degrade the organic matters in sewage and decompose the organic matters into small molecular substances, such as water and CO2And the like, thereby achieving the purpose of sewage treatment. However, the advanced oxidation process also has limitations, for example, semiconductor photocatalysis technology is not high in light energy utilization rate and is affected by light transmittance in sewage, and besides, the recovery of photocatalytic materials is difficult, so that a method for more effectively degrading organic pollutants in sewage is urgently sought, and a method for degrading organic pollutants by using a magnetocaloric-pyroelectric material is proposed.
The pyroelectric material has a pyroelectric effect, can convert heat energy into electric energy, can generate positive and negative charges under external thermal excitation (such as temperature difference change of room temperature) to output, degrades organic pollutants by analogy with photocatalysis of semiconductors, and has the catalytic potential by utilizing the alternating change of cold and heat. The absorption and release of the surface charge of the sewage treatment device can lead the sewage treatment device to carry out redox reaction with a surface receptor to generate active free radicals with strong oxidizing property for degrading organic matters in the sewage.
However, in our daily life, the temperature change rate and the temperature change range are limited, and are greatly influenced by the environment, and if the temperature change only depends on the natural environment, the catalytic degradation rate of the pyroelectric material is limited, and the practical application range of the pyroelectric material is greatly limited. Therefore, the problem that the constraint of the external environment can be released, a heat source with required cold and hot alternation can be generated, and the process of artificially regulating and degrading organic matters is urgently needed to be solved is searched for the pyroelectric material.
The magnetocaloric material can convert magnetic energy into heat energy under the action of an alternating magnetic field, and the change of temperature can be obtained only by applying the alternating magnetic field to the material, which is a process of absorbing the magnetic energy, converting the magnetic energy into the heat energy and dissipating the heat energy. The magnetocaloric material and the pyroelectric material are combined to prepare the magnetocaloric-pyroelectric nano material, so that the magnetocaloric-pyroelectric multi-physical field coupling is realized, and the huge challenge of degrading organic matters by the pyroelectric material at present is hopefully solved.
Disclosure of Invention
In view of the above problems in the prior art, the applicant of the present invention provides a preparation method and an application of a magnetocaloric-pyroelectric composite material. The nano material is used for a novel method for degrading organic pollutants, and realizes a magnetic field induced pyroelectric catalytic effect by utilizing magnetic-thermal-electric multi-physical field coupling. The prepared pyroelectric material has good stability, and the prepared material contains the magnetocaloric material and can be recycled by using a magnet, so that the loss of a powder sample is small, the powder sample can be repeatedly used for many times, and the recycling rate is high.
The technical scheme of the invention is as follows:
a composite material, which is a magnetocaloric material and a pyroelectric material; the magnetocaloric material is at least one of iron, iron alloy, cobalt alloy, nickel alloy, iron oxide, cobalt oxide and nickel oxide, rare earth element and rare earth-Mn-based perovskite compound or giant magnetocaloric material; the pyroelectric material is Ba0.7Sr0.3TiO3、Bi0.5Na0.5TiO3、BaTiO3、LiTaO3、LiNbO3、KNbO3、NaNbO3、BiFeO3、Pb(Zr,Ti)O3、GaN、ZnSnO3、ZnO、PbTiO3At least one of lead magnesium niobate, polyvinylidene fluoride or polyvinylidene fluoride.
The molar ratio of the magnetocaloric material to the pyroelectric material is 1: 1-1: 6.
the iron alloy, the cobalt alloy and the nickel alloy are Fe50Co50、Fe51Rh49、Fe93.57Si6.43Or Ni2(Mn90V10) At least one of Sn; the iron oxide, the cobalt oxide and the nickel oxide are beta-Fe2O3、Fe3O4、MnFe2O4、ZnFe2O4、CoFe2O4Or NiFe2O4At least one of; the rare earth element and the rare earth-Mn-based perovskite compound are Nd, Tb, Dy, Ho, Er, Tm, Gd and La1-xSrxMnO3、(La67Ba33)MnO3、(La90Na10)MnO3Or (La)65Y5Sr30)MnO3At least one of; the giant magnetocaloric material is Gd5(Si2Ge2) Or LaFe11.2Co0.7Si1.1At least one of (1).
The La1-xSrxMnO3Wherein x is in the range of 0<x<1。
The composite material is in a core-shell shape, a column shape, a layer shape or a composite nanotube array; the core-shell-shaped core layer is made of a magnetocaloric material, and the shell layer is made of a pyroelectric material.
The composite material is compounded by adopting a sol-gel method, and the specific compounding method comprises the following steps:
using a magnetocaloric material as La1-xSrxMnO3The pyroelectric material is Ba0.7Sr0.3TiO3For example, the following steps are carried out:
la1-xSrxMnO3Dispersing the nano particles in ethylene glycol, adding tetrabutyl titanate, fully stirring and uniformly mixing to obtain a suspension, and then drying at 60-90 ℃ to obtain powder; dissolving strontium nitrate and barium nitrate in water according to the element molar ratio of 0.7:0.3, adding the dried powder into the water, fully stirring, carrying out hydrothermal reaction at the temperature of 150-1-xSrxMnO3@Ba0.7Sr0.3TiO3A nanometer core-shell structure composite material.
The composite material can be compounded by adopting a sol-gel method, and the specific compounding method comprises the following steps:
the magnetocaloric material is beta-Fe2O3The pyroelectric material is PbTiO3For example, the following steps are carried out:
beta-Fe2O3Dispersing nano particles in ethylene glycol, adding tetrabutyl titanate, fully stirring and uniformly mixing to obtain a suspension, drying at 60-90 ℃ to obtain powder, adding the dried powder into a lead nitrate solution, fully stirring, carrying out hydrothermal reaction at the temperature of 150-180 ℃, washing, drying and calcining after the reaction is finished, and keeping the temperature for 2-4 h at the calcining temperature of 700-750 ℃ to finally obtain beta-Fe2O3@PbTiO3A nanometer core-shell structure composite material.
The composite material can be compounded by a hydrothermal method, and the specific compounding method comprises the following steps:
the magnetocaloric material is cobalt powder, and the thermolytic material is PbTiO3For example, the following steps are carried out:
ultrasonically dispersing cobalt powder in solution dissolved with polyethylene glycol-600Adding urea and a titanium sulfate solution in sequence, stirring and uniformly mixing for 2-3 h at the temperature of 60-80 ℃, then washing with ethanol and water respectively, and drying to obtain Co @ Ti (OH)2Coating the product, followed by adding Co @ Ti (OH)2Dissolving the coated product and lead nitrate in deionized water, transferring the solution into a reaction kettle, washing and drying the solution after hydrothermal reaction, and then preserving the temperature for 2-3 h at 600-650 ℃ to finally obtain Co @ PbTiO3A nanometer core-shell structure composite material.
The composite material can be compounded by adopting a microwave sintering method, and the specific compounding method comprises the following steps:
the pyroelectric material is BiFeO3The magnetocaloric material is CoFe2O4For example, the following steps are carried out:
taking a raw material Bi2O3，Fe2O3，CO3O4Drying in an oven at 100-120 ℃ for 10-12 h, and drying the dried Bi2O3And Fe2O3Taking out the raw materials, mixing, sieving, and then preserving heat in a muffle furnace at 700-750 ℃ for 10-12 h to obtain BiFeO3Performing secondary ball milling and granulation on the powder to obtain BiFeO3Powder; drying the Fe2O3And CO3O4Mixing the raw materials according to a mass ratio, sieving, then preserving heat in a muffle furnace at 950-1000 ℃ for 4-5 h, and then carrying out secondary ball milling and granulation to obtain CoFe2O4Powder according to BiFeO3、CoFe2O4With BiFeO3The materials are sequentially put into a circular die with the diameter of 10mm, pressed into layers under the pressure of 200-250 MPa, and the pressed composite material is kept at the temperature of 900-950 ℃ for 2-3 h to obtain (1-x) BiFeO3/xCoFe2O4A sandwich-like layered composite wherein x is 0.2, 0.4, 0.6 or 0.8.
The use of the composite material in the degradation of organic contaminants.
The beneficial technical effects of the invention are as follows:
the heat source in the invention is stable, is not from the temperature difference change heat energy of the room temperature, but from the temperature change generated by the magnetocaloric effect, and realizes the magnetic-thermal-electric multi-physical field coupling in the whole degradation process of the organic matters. Compared with the energy conversion efficiency of a photoelectric material used in photocatalysis, the energy conversion efficiency of the pyroelectric material is higher, and the catalytic efficiency is expected to be improved. In addition, the pyroelectric material has good stability, and the prepared material contains the magnetocaloric material and can be recycled by using a magnet, so that the powder sample has low loss, can be repeatedly used for many times and has high recycling rate.
The magnetocaloric-pyroelectric material can have various communication modes, and can be roughly divided into the following categories, as shown in fig. 1: one is particle composite, two phases are uniformly distributed in the composite material in the form of micron-sized particles, and the coupling between the two phases occurs between macro and micro; one is laminar composite, two phases are alternately superposed in a single-layer form; one is nanocomposite, due to the large differences in properties and macroscopically exhibited in the nanoscale range; yet another is columnar compounding.
Fig. 2 illustrates the principle of the magnetocaloric-pyroelectric nano core-shell structure material degrading organic pollutants by taking a specific magnetocaloric-pyroelectric nano core-shell structure material as an example. La is selected among these1-xSrxMnO3(LSMO) nano-particles are used as core materials of core-shell structures, and pyroelectric materials Ba are used1-xSrxTiO3(BST) is wrapped on the LSMO core to prepare the LSMO @ BST nano core-shell structure with a complete structure.
The preparation of the magnetocaloric-pyroelectric material into a nano core-shell structure has many advantages, such as: the core-shell structure ensures mutual isolation between the magnetocaloric materials and communication between the pyroelectric materials, thereby ensuring the insulating property of the whole sample, ensuring a larger interface area between two phases, and generating a large magnetoelectric coupling effect by the large interface area.
As shown in fig. 2, when an alternating magnetic field is applied, the temperature of the LSMO core changes with the change of the magnetic field strength due to the magnetocaloric effect, and the change is transferred to the external BST shell, and the pyroelectric material has the capability of converting thermal energy into electric energy, so that the BST surface generates positive and negative charges, and the occurrence of the positive and negative charges can cause some changesBy redox reactions, generating reactive radicals with strong oxidizing properties, e.g.. OH, O2 -These strongly oxidizing substances can degrade organic pollutants to small molecule substances, such as CO2Water, etc. to reach the aim of degrading sewage.
Drawings
Fig. 1 is a schematic diagram of several communication modes of magnetocaloric-pyroelectric materials.
Fig. 2 is a schematic diagram of a catalytic effect of a specific magnetocaloric-pyroelectric nano core-shell structure material.
FIG. 3 is a schematic diagram of the preparation of LSMO @ BST nano core-shell structure material.
FIG. 4 is a graph of the UV-VIS absorption spectrum of RhB solution at different times.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
In this embodiment, the magnetocaloric-pyroelectric nano core-shell structure material is taken as an example, La0.7Sr0.3MnO3(LSMO) nanoparticles as core material of core-shell structure, Ba0.7Sr0.3TiO3(BST) is a shell layer, a magnetocaloric material is synthesized by a sol-gel method, and then a pyroelectric material shell layer is wrapped outside the magnetocaloric material by a hydrothermal method, and a preparation diagram thereof is shown in fig. 3.
La0.7Sr0.3MnO3Preparation of (LSMO): lanthanum nitrate, strontium nitrate and manganese nitrate are used as raw materials, dissolved in deionized water according to a molar ratio of 0.7:0.3:1, and the ratio of metal ions: citric acid: adding citric acid and ethylene glycol according to the proportion of 1:1.5:1.5, vigorously stirring, adding ammonia water to adjust the pH value to 9, presintering at 300 ℃ for 30min, annealing at 950 ℃ for 4h, and growing LSMO particles with good crystallization performance and obvious magnetocaloric effect.
Preparing an LSMO @ BST nano core-shell structure material: ultrasonically dispersing LSMO nano particles in ethylene glycol, adding tetrabutyl titanate into the ethylene glycol, fully stirring, drying the obtained suspension at 90 ℃, dissolving strontium nitrate and barium nitrate into deionized water according to the element molar ratio of 0.7:0.3, adding the dried powder into the suspension, fully stirring, transferring the mixture into a reaction kettle for hydrothermal reaction at 180 ℃, and then carrying out heat treatment to obtain the sample. The core-shell structures with different shell thicknesses can be obtained by adjusting the molar ratio of the magnetocaloric material to the pyroelectric material.
Example 2
In this embodiment, taking a magnetocaloric-pyroelectric nanotube material as an example, an anodic oxidation method is used to prepare a porous alumina template (AAO template), and a sol-gel method is used to synthesize La in nanopores of the AAO template0.7Sr0.3MnO3@Ba0.7Sr0.3TiO3An array of nanotubes.
Preparation of AAO template: and (3) adopting the aluminum foil with the mass fraction higher than 99.999%, and sequentially carrying out cutting, annealing, polishing and other treatments to obtain the pretreated aluminum foil. And (3) performing electrochemical oxidation by taking 0.3mol/L oxalic acid solution as electrolyte, aluminum foil as an anode and a carbon rod as a cathode, oxidizing for 2-10 hours each time, removing a formed aluminum oxide film by using a mixed solution of phosphoric acid and chromium oxide after the first oxidation, washing the aluminum oxide film by using distilled water, and performing the second oxidation under the same oxidation condition as the first step to finally obtain the transparent AAO template.
Preparation of LSMO @ BST nanotube array: lanthanum nitrate, strontium nitrate, manganese nitrate, barium nitrate and tetrabutyl titanate are used as raw materials, are dissolved in ethylene glycol monomethyl ether according to a corresponding stoichiometric ratio, then glacial acetic acid is added, the mixture is fully stirred to be completely dissolved, then a proper amount of acetic anhydride is added for dehydration, the solution is continuously stirred until the solution is cooled, then a proper amount of ethanolamine is added to adjust the viscosity of the solution, and finally a proper amount of ethylene glycol monomethyl ether is added to adjust the concentration of the solution to 0.3 mol/L. And (3) pouring the prepared gel into the prepared AAO template by adopting a vacuum negative pressure pouring method, repeating for several times, and finally annealing the AAO template poured with the gel at 600 ℃ for 10 hours to obtain the LSMO @ BST nanotube array.
Example 3
In this embodiment, the pyroelectric nanoparticles are uniformly dispersed in the magnetocaloric material, the magnetocaloric material nanoparticles with good dispersibility are synthesized by a sol-gel method, and then the magnetocaloric material nanoparticles are dispersed in the gel of the pyroelectric material, and the magnetocaloric material is La0.7Sr0.3MnO3(LSMO) nanoparticles, the pyroelectric material being Ba0.7Sr0.3TiO3(BST) nanoparticles.
Lanthanum nitrate, strontium nitrate and manganese nitrate are used as raw materials, dissolved in deionized water according to a molar ratio of 0.7:0.3:1, and the ratio of metal ions: citric acid: adding citric acid and ethylene glycol according to the proportion of 1:1.5:1.5, vigorously stirring, adding ammonia water to adjust the pH value to 9, presintering at 300 ℃ for 30min, annealing at 950 ℃ for 4h, and growing LSMO particles with good crystallization performance and obvious magnetocaloric effect. Strontium nitrate, barium nitrate and tetrabutyl titanate are used as raw materials, gel is prepared, the prepared LSMO particles are added into the prepared BST gel, the mixture is continuously stirred in water bath at 80 ℃ to form dry gel, the dry gel is dried in an oven at 140 ℃, then the annealing is carried out for 2h at 400 ℃, then the calcination is carried out for 2h at 700 ℃, the powder is pressed into a wafer and then the annealing is carried out for 5h at 700 ℃, a magnetocaloric-pyroelectric powder sample is obtained, and the pyroelectric particles are uniformly dispersed in the magnetocaloric particles.
Example 4
In this embodiment, the magnetocaloric material and the pyroelectric material are sandwiched and have a layered structure, and the pyroelectric material is BiFeO3(BFO) magnetocaloric material CoFe2O4(CFO), a microwave sintering method is adopted to synthesize the layered magnetoelectric composite material (1-x) BFO/xCFO, wherein x is 0.2, 0.4, 0.6 and 0.8.
Preparing a raw material Bi2O3，Fe2O3，CO3O4Accurately weighing the raw materials according to the required stoichiometric ratio, and drying in an oven at 120 ℃ for 12 h. Drying the Bi2O3And Fe2O3Taking out the raw materials, mixing, sieving, and presintering (namely keeping the temperature in a muffle furnace at 750 ℃ for 12 hours) to obtain BiFeO3Performing secondary ball milling and granulation on the powder to obtain BiFeO3And (5) preparing the powder for later use. Similarly, the dried Fe2O3And CO3O4Mixing the raw materials, sieving, pre-sintering (keeping the temperature in a muffle furnace at 1000 ℃ for 5h), performing secondary ball milling and granulating to obtain CoFe2O4And (5) preparing the powder for later use. And weighing BFO and CFO powder in proportion, putting the BFO, CFO and BFO powder into a circular die with the diameter of 10mm in sequence, pressing the BFO, CFO and BFO powder into a layer under 250MPa, and preserving the heat of the pressed composite material for 3 hours at 950 ℃ to obtain the sandwich-shaped layered composite material.
Test example 1
The LSMO @ BST nano core-shell structure material obtained in example 1 is taken for the research of degrading organic pollutants: taking 50mg of the prepared nano core-shell structure material, placing the material in 50mL of rhodamine B (5mg/L) RhB solution, placing a beaker in the center of a high-frequency magnetic field generator, adjusting the size and frequency of a magnetic field, recording the temperature of the liquid solution once every minute until the temperature is stable, then closing the magnetic field to naturally reduce the temperature of the solution to room temperature, then opening the magnetic field again, sampling the solution once every 5 cycles, testing the absorption intensity of the sample solution at 554nm by using an ultraviolet spectrophotometer, and as shown in the result of figure 4, the intensity of the maximum absorption peak of the rhodamine B solution at 554nm is smaller and smaller along with the increase of time, which indicates that the prepared LSMO @ BST nano core-shell structure material can realize the degradation of the RhB solution. The materials prepared in examples 2-4 have similar properties for degrading organic waste and are not described in detail herein.
Claims (10)
1. The composite material is characterized in that the composite material is a magnetocaloric material and a pyroelectric material; the magnetocaloric material is at least one of iron, iron alloy, cobalt alloy, nickel alloy, iron oxide, cobalt oxide and nickel oxide, rare earth element and rare earth-Mn-based perovskite compound or giant magnetocaloric material; the pyroelectric material is Ba0.7Sr0.3TiO3、Bi0.5Na0.5TiO3、BaTiO3、LiTaO3、LiNbO3、KNbO3、NaNbO3、BiFeO3、Pb(Zr,Ti)O3、GaN、ZnSnO3、ZnO、PbTiO3At least one of lead magnesium niobate, polyvinylidene fluoride or polyvinylidene fluoride.
2. The composite material of claim 1, wherein the molar ratio of the magnetocaloric material to the pyroelectric material is 1: 1-1: 6.
3. the composite material of claim 1, wherein the iron, cobalt and nickel alloys are Fe50Co50、Fe51Rh49、Fe93.57Si6.43Or Ni2(Mn90V10) At least one of Sn; the iron oxide, the cobalt oxide and the nickel oxide are beta-Fe2O3、Fe3O4、MnFe2O4、ZnFe2O4、CoFe2O4Or NiFe2O4At least one of; the rare earth element and the rare earth-Mn-based perovskite compound are Nd, Tb, Dy, Ho, Er, Tm, Gd and La1-xSrxMnO3、(La67Ba33)MnO3、(La90Na10)MnO3Or (La)65Y5Sr30)MnO3At least one of; the giant magnetocaloric material is Gd5(Si2Ge2) Or LaFe11.2Co0.7Si1.1At least one of (1).
4. The composite material of claim 3, wherein the La1-xSrxMnO3Wherein x is in the range of 0<x<1。
5. The composite material of claim 1, wherein the composite material is in the form of a core-shell, a pillar, a layer, or a composite nanotube array; the core-shell-shaped core layer is made of a magnetocaloric material, and the shell layer is made of a pyroelectric material.
6. A preparation method of the composite material as claimed in any one of claims 1 to 5, characterized in that the composite material is compounded by a sol-gel method, and the specific compounding method is as follows:
using a magnetocaloric material as La1-xSrxMnO3The pyroelectric material is Ba0.7Sr0.3TiO3For example, the following steps are carried out:
la1-xSrxMnO3Dispersing the nano particles in ethylene glycol, adding tetrabutyl titanate, fully stirring and uniformly mixing to obtain a suspension, and then drying at 60-90 ℃ to obtain powder; dissolving strontium nitrate and barium nitrate in water according to the element molar ratio of 0.7:0.3, adding the dried powder into the water, fully stirring, carrying out hydrothermal reaction at the temperature of 150-1-xSrxMnO3@Ba0.7Sr0.3TiO3A nanometer core-shell structure composite material.
7. A method for preparing the composite material according to any one of claims 1 to 5, wherein the composite material can be compounded by a sol-gel method, and the specific compounding method is as follows:
the magnetocaloric material is beta-Fe2O3The pyroelectric material is PbTiO3For example, the following steps are carried out:
beta-Fe2O3Dispersing nano particles in ethylene glycol, adding tetrabutyl titanate, fully stirring and uniformly mixing to obtain a suspension, drying at 60-90 ℃ to obtain powder, adding the dried powder into a lead nitrate solution, fully stirring, carrying out hydrothermal reaction at the temperature of 150-180 ℃, washing, drying and calcining after the reaction is finished, and keeping the temperature for 2-4 h at the calcining temperature of 700-750 ℃ to finally obtain beta-Fe2O3@PbTiO3A nanometer core-shell structure composite material.
8. Method for preparing a composite material according to claims 1-5, characterized in that the composite material can be compounded by hydrothermal method, and the specific compounding method is as follows:
the magnetocaloric material is cobalt powder, and the thermolytic material is PbTiO3For example, the following steps are carried out:
ultrasonically dispersing cobalt powder in a solution in which polyethylene glycol-600 is dissolved, sequentially adding urea and titanium sulfate solution, stirring and uniformly mixing for 2-3 h at the temperature of 60-80 ℃, then respectively washing with ethanol and water, and drying to obtain Co @ Ti (OH)2Coating the product, followed by adding Co @ Ti (OH)2Dissolving the coated product and lead nitrate in deionized water, transferring the solution into a reaction kettle, washing and drying the solution after hydrothermal reaction, and then preserving the temperature for 2-3 h at 600-650 ℃ to finally obtain Co @ PbTiO3A nanometer core-shell structure composite material.
9. The method for preparing the composite material according to the above claims 1-5, wherein the composite material can be compounded by microwave sintering, and the specific compounding method is as follows:
the pyroelectric material is BiFeO3The magnetocaloric material is CoFe2O4For example, the following steps are carried out:
taking a raw material Bi2O3，Fe2O3，CO3O4Drying in an oven at 100-120 ℃ for 10-12 h, and drying the dried Bi2O3And Fe2O3Taking out the raw materials, mixing, sieving, and then preserving heat in a muffle furnace at 700-750 ℃ for 10-12 h to obtain BiFeO3Performing secondary ball milling and granulation on the powder to obtain BiFeO3Powder; drying the Fe2O3And CO3O4Mixing the raw materials according to a mass ratio, sieving, then preserving heat in a muffle furnace at 950-1000 ℃ for 4-5 h, and then carrying out secondary ball milling and granulation to obtain CoFe2O4Powder according to BiFeO3、CoFe2O4With BiFeO3The materials are sequentially put into a circular die with the diameter of 10mm, pressed into layers under the pressure of 200-250 MPa, and the pressed composite material is kept at the temperature of 900-950 ℃ for 2-3 h to obtain (1-x) BiFeO3/xCoFe2O4A sandwich-like layered composite material whereinx is 0.2, 0.4, 0.6 or 0.8.
10. Use of a composite material according to any one of claims 1 to 5 for the degradation of organic contaminants.
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| CN114108022B (en) * | 2021-11-22 | 2023-05-30 | 辽宁大学 | Heterojunction KNbO 3 /ZnFe 2 O 4 Preparation method and application of photoelectrode film |
| CN114572968A (en) * | 2022-02-22 | 2022-06-03 | 金华职业技术学院 | ZrNb2O6/ZrO2-CNTs composite powder and preparation method thereof |
| CN114572968B (en) * | 2022-02-22 | 2023-09-08 | 金华职业技术学院 | ZrNb (ZrNb) 2 O 6 /ZrO 2 -CNTs composite powder and preparation method thereof |
| CN114832825A (en) * | 2022-05-18 | 2022-08-02 | 东南大学 | Preparation method of catalyst with spherical shell separation double-coating structure |
| CN114832825B (en) * | 2022-05-18 | 2024-02-09 | 东南大学 | Preparation method of spherical shell separation double-coating structure catalyst |
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