CN114100600A - Perovskite material and preparation method and application thereof - Google Patents
Perovskite material and preparation method and application thereof Download PDFInfo
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- CN114100600A CN114100600A CN202010889906.9A CN202010889906A CN114100600A CN 114100600 A CN114100600 A CN 114100600A CN 202010889906 A CN202010889906 A CN 202010889906A CN 114100600 A CN114100600 A CN 114100600A
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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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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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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- B01J35/60—
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- B01J35/613—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/36—Reactivation or regeneration
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G27/00—Compounds of hafnium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G27/00—Compounds of hafnium
- C01G27/006—Compounds containing, besides hafnium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
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Abstract
The application discloses a perovskite material and a preparation method and application thereof, wherein the structural formula of the material is ABO3Wherein A is selected from at least one of Ca, Sr and Ba, and B is selected from at least one of Zr, Ti and Hf; the perovskite material has a porous structure. The specific surface area of the perovskite material is 1.73-4.63 times of that of the conventional perovskite material, and the perovskite material is subjected to catalytic wet oxidationThe process for regenerating the activated carbon has excellent catalytic regeneration effect. The perovskite material has simple preparation process and easy control, and the specific surface area is far larger than that of perovskite powder prepared by the traditional method.
Description
Technical Field
The application relates to a perovskite material and a preparation method and application thereof, belonging to the technical field of inorganic nano materials.
Background
The regeneration treatment of the waste activated carbon, the realization of resource utilization and environmental pollution control are the problems which need to be solved urgently at present. Compared with other regeneration methods, such as pyrolysis regeneration, chemical solvent regeneration, electrochemical regeneration, microwave radiation regeneration and the like, the catalytic wet oxidation regeneration process has universality and can effectively reduce NOX、SOXThe regeneration technology has the advantages of good environmental protection benefit and high regeneration efficiency, is an efficient, time-saving and energy-saving regeneration technology, and has infinite development potential and advantages. In the process, the reaction temperature of about 200 ℃ has certain requirements on the thermal stability and the chemical stability of the catalyst, and the catalyst is required to have certain activity.
Perovskite type composite oxide ABO3The material is a novel inorganic non-metallic material with unique physical properties and chemical properties, has the characteristics of good catalytic activity, ferromagnetism, electric conductivity and the like, and is a novel functional material with various purposes. Related studies have shown that perovskite-type materials have excellent catalytic properties in catalytic wet oxidation systems. LaFeO was investigated as in DOI 10.1016/j apcatb.2018.12.0243The catalyst realizes the high-efficiency degradation of acrylic acid by catalytic wet oxidation through A-site doping. At present, the main preparation methods for synthesizing perovskite type oxides include the traditional high-temperature solid phase method (ceramic process method), the sol-gel method, the hydrothermal synthesis method, the high-energy ball milling method and the precipitation method, and in addition, the vapor deposition method, the supercritical drying method, the micro-emulsion method, the self-propagating high-temperature combustion synthesis method and the like. The material prepared by the method has small specific surface area, and the application of the perovskite material is greatly limited, so that how to improve the specific surface area of the perovskite material becomes a hotspot of research.
LaMnO of high specific surface area obtained by acid etching in patent CN 107456964A3The material not only can generate a large amount of acidic wastewater to bring about the subsequent wastewater treatment problem, but also can cause metal loss and reduce the stability of the catalyst. The hydrothermal carbon microsphere has stable chemical property and good thermal stability, and simultaneously the surface of the hydrothermal carbon microsphere contains rich oxygen-containing functional groups, so that the hydrothermal carbon microsphere can be used with various types of functional groupsThe other functional groups combine with each other to form a novel composite material. Therefore, the carbon spheres can be used as carriers to load metal precursors to generate the perovskite material in situ. The carbon ball template overflows in a gas form in the high-temperature pyrolysis process, and can further play a role in pore-forming and pore-expanding, so that the specific surface area of the perovskite material is effectively improved.
Disclosure of Invention
According to a first aspect of the present application, there is provided a perovskite material with a large specific surface area, having the formula ABO3The perovskite material has the specific surface area 1.73-4.63 times that of the conventional perovskite material, and has a better catalytic regeneration effect in a catalytic wet oxidation activated carbon regeneration process. The perovskite material has simple preparation process and easy control, and the specific surface area is far larger than that of perovskite powder prepared by the traditional method.
A perovskite material with a structural formula of ABO3Wherein A is selected from at least one of Ca, Sr and Ba, and B is selected from at least one of Zr, Ti and Hf;
the perovskite material has a porous structure.
In the present application, the perovskite material has a porous structure, and has a loose porous structure and a large specific surface area for the perovskite material as a whole.
Optionally, the perovskite material has a specific surface area of 20-100 m2/g。
Optionally, the perovskite material has a specific surface area of 30-100 m2/g。
In a second aspect of the present application, a method for preparing a perovskite material is provided, which at least comprises the following steps:
(1) carrying out reaction I on a mixed solution I consisting of a carbon source and water to obtain carbon nanospheres;
(2) carrying out a reaction II on a mixed solution II containing acid and the nano carbon spheres to obtain acid modified carbon spheres;
(3) carrying out a reaction III on a mixed solution III containing the acid modified carbon spheres, a metal source A and a metal source B, and obtaining precursor microspheres by utilizing an electrostatic effect and in-situ surface hydrolysis;
(4) and calcining the precursor microspheres to obtain the perovskite material.
Optionally, the carbon source in step (1) is at least one selected from glucose, fructose, sucrose and starch.
Optionally, the concentration of the carbon source in the mixed solution I is 0.3-0.7 mol/L.
Optionally, the lower limit of the concentration of the carbon source in the mixed solution I is selected from 0.3mol/L, 0.4mol/L, 0.5mol/L and 0.6mol/L, and the upper limit is selected from 0.4mol/L, 0.5mol/L, 0.6mol/L and 0.7 mol/L.
Alternatively, specific conditions for the reaction i include:
the hydrothermal reaction temperature is 160-190 ℃, and 190 ℃ is preferred;
the hydrothermal reaction time is 4-12 h, preferably 6 h.
Optionally, the acid in step (2) is at least one of nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid, preferably nitric acid.
Optionally, the content of the acid in the mixed solution II is 0.5-6 mol/L.
Optionally, the content of the acid in the mixed solution II is 0.5-2 mol/L.
Preferably, the content of the acid in the mixed liquid II is 1 mol/L.
Optionally, the content of the carbon nanospheres in the mixed liquid II is 2-10 g/L.
Optionally, the lower limit of the content of the carbon nanospheres in the mixed solution II is selected from 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L and 9g/L, and the upper limit is selected from 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L and 10 g/L.
Preferably, the solvent in the mixed solution II is water.
Alternatively, the specific conditions of the reaction II comprise:
the reaction temperature is 10-40 ℃;
the reaction time is 12-48 h.
Optionally, the A metal source in the step (3) is at least one of Ca nitrate, Sr nitrate and Ba nitrate.
Optionally, the B metal source is at least one of Zr nitrate, Ti nitrate, Hf nitrate.
Optionally, the molar ratio of the a metal source to the B metal source is 1:1 to 1.5, wherein the molar amount of the A metal source is calculated by the molar amount of the A metal, and the molar amount of the B metal source is calculated by the molar amount of the B metal.
Optionally, the lower limit of the molar ratio of the metal source A to the metal source B is 1:1.5, 1: 1.4, 1: 1.2, 1: 1.1, upper limit 1: 1.4, 1: 1.2, 1: 1.1 and 1:1.
Optionally, the mass ratio of the acid-modified carbon spheres to the metal source is 0.9-50: 1, wherein the metal source is the sum of the metal source A and the metal source B.
Optionally, the lower limit of the mass ratio of the acid-modified carbon spheres to the metal source is selected from 0.9, 3, 6 and 12, and the upper limit is selected from 3, 6, 12 and 43.
Optionally, the solvent in the mixed solution III is water;
optionally, the concentration of the metal source A in the mixed liquid III is 0.001-0.01 mol/L.
Optionally, the lower limit of the concentration of the A metal source in the mixed liquid III is selected from 0.00125mol/L, 0.0015mol/L, 0.0025mol/L, 0.005mol/L and 0.0075mol/L, and the upper limit is selected from 0.0015mol/L, 0.0025mol/L, 0.005mol/L, 0.0075mol/L and 0.01 mol/L.
Alternatively, specific conditions of the reaction iii include:
the reaction temperature is 20-40 ℃;
the reaction time is 6-24 h.
Optionally, the removing the acid-modified carbon spheres in the precursor microspheres specifically includes:
roasting for 2-6 h at 300-500 ℃, and then heating to 700-900 ℃ for 2-10 h.
Alternatively, the specific conditions of the calcination include: roasting for 2-6 h at 300-500 ℃, and then heating to 700-900 ℃ for 2-10 h.
In the application, the carbon nanospheres, the carbon microsphere templates and the carbon microsphere particles have the same meaning and all refer to carbon spheres synthesized by a carbon source through a hydrothermal method.
In a third aspect of the application, at least one of the perovskite material and the perovskite material prepared by the preparation method is applied to activated carbon regeneration by a catalytic wet oxidation method.
The beneficial effects that this application can produce include:
(1) the preparation process is simple and easy to control, and the synthesis process is green and environment-friendly;
(2) the specific surface area of the obtained perovskite is far larger than that of perovskite powder prepared by the traditional method;
(3) the obtained product has uniform size, high purity and easy regulation and control of the preparation process;
(4) compared with perovskite powder materials, the obtained product has excellent effect in the process of regenerating activated carbon by catalytic wet oxidation.
Drawings
FIG. 1 is a scanning electron micrograph (100nm) of a carbon sphere template prepared in example 1;
FIG. 2 is a scanning electron microscope image of the precursor microspheres prepared in examples 1-4, wherein (1) corresponds to example 1(200nm), (2) corresponds to example 2(200nm), (3) corresponds to example 3(100nm), and (4) corresponds to example 4(200 nm);
FIG. 3 is a scanning electron micrograph (100nm) of the product prepared in example 3;
FIG. 4 is a graph showing N of the products prepared in example 3 and comparative examples 1 to 32Adsorption-desorption isotherm diagram;
FIG. 5 is a scanning electron microscope photograph of the products prepared in comparative examples 1 to 3, wherein (1) corresponds to comparative example 1(1 μm), (2) corresponds to comparative example 2(1 μm), and (3) corresponds to comparative example 3(1 μm);
FIG. 6 is an X-ray diffraction pattern of the products prepared in example 3 and comparative examples 1-3;
FIG. 7 is a graph showing the regeneration efficiency of the products prepared in example 3 and comparative examples 1 to 3 in the process of regenerating activated carbon by catalytic wet oxidation.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
As a specific embodiment, a method of preparing a perovskite material, comprises:
(1): preparing a carbon sphere template with uniform size by using glucose as a raw material and deionized water as a solvent through a hydrothermal method, and separating and cleaning the carbon sphere template;
the preparation of the monodisperse carbon spheres by the hydrothermal method comprises the steps of dissolving anhydrous glucose powder in deionized water at room temperature, uniformly mixing by ultrasonic waves, taking part of the solution, placing the solution in a 100mL hydrothermal kettle, heating the solution for a certain time at a certain temperature, and naturally cooling the solution to the room temperature to obtain a dark brown solid-liquid mixture.
Wherein the concentration of the glucose solution is 0.3-0.7 mol/L, and the filling degree of the kettle is 60-80%; the hydrothermal temperature is 160-190 ℃; the hydrothermal time is 4-12 h.
The step of separating and cleaning the carbon spheres is to perform solid-liquid separation on a solid-liquid mixture obtained after hydrothermal treatment by using a centrifuge, and respectively perform ultrasonic cleaning and washing on the obtained dark brown solid product for 2-3 times by using deionized water and absolute ethyl alcohol; drying the washed solid product at 60-90 ℃ for 5-8 h, cooling to room temperature, and grinding to obtain monodisperse carbon spheres;
wherein the rotating speed of the centrifuge is more than 8000rpm/min during solid-liquid separation, and the centrifugation time is 8-10 min.
(2): properly modifying the carbon sphere template;
the surface modification of the carbon spheres is to dilute 68 wt% nitric acid and prepare a nitric acid solution with the concentration of 1 mol/L; adding the carbon spheres prepared in the step (1) into a nitric acid solution with the concentration of 1mol/L, uniformly mixing, standing for 24h, washing with deionized water and absolute ethyl alcohol respectively, centrifuging, and drying at the temperature of 60-80 ℃ to obtain acid modified carbon spheres;
wherein, 1mol/L HNO3The adding amount of carbon spheres in the solution is 2 to10g/L。
(3): preparing a precursor solution, adding a carbon sphere template, and preparing precursor microspheres by utilizing an electrostatic effect and in-situ surface hydrolysis;
the preparation method of the precursor comprises the following steps:
3.1. weighing metal nitrates with different masses according to the molar ratio of the two metal elements, and adding deionized water to prepare a nitrate mixed solution;
wherein, the metal A is one or more of Ca, Sr and Ba, and the metal B is one or more of Zr, Ti and Hf; the molar ratio of the metal elements at the A site and the B site is 1: 1-1: 1.5; the volume of the metal nitrate solution is 20-40 mL.
3.2. Weighing a certain amount of the modified carbon spheres obtained in the step (2), adding the carbon spheres into the nitrate mixed solution obtained in the step (3.1), and then performing ultrasonic dispersion to obtain a black brown suspension;
wherein the mass ratio of the carbon spheres to the metal nitrate is 0.9324: 1-42.37: 1.
3.3. Ultrasonically dispersing the suspension obtained in the step 3.2 uniformly, stirring for a certain time at a constant temperature, taking out, and naturally cooling to room temperature to obtain a black brown suspension;
wherein the constant temperature reaction temperature is 20-40 ℃, and the constant temperature reaction time is 6-24 h.
3.4. Drying the black brown suspension obtained in the step 3.3 in an oven at 60-80 ℃ for 4-6 h, cooling to room temperature, and grinding to obtain a precursor product;
(4): and removing the central carbon core after high-temperature calcination to obtain the nano hollow spherical perovskite material.
And (3) placing the precursor microspheres obtained in the step (3) in a muffle furnace, roasting at 300-500 ℃ for 4h, then heating to 700-900 ℃ for 4h at the heating rate of 1-3 ℃/min, and finally naturally cooling to room temperature to obtain the perovskite material with the large specific surface area.
In the examples, the characterization and analysis of the samples was as follows:
the morphological characteristics of the sample are analyzed through a Scanning Electron Microscope (SEM) test, the analysis instrument is a JSM6360LV scanning electron microscope, and the performance indexes are as follows: accelerating voltage is 0.5-30 kV, and amplification factor is as follows: 18-50000 times, resolution: high vacuum of 3.0nm and low vacuum of 4.5 nm. Attached energy spectroscopy and EBSD analysis systems.
The structural characteristics of the sample were analyzed by X-ray diffraction pattern (XRD) measurement using a powder X-ray diffractometer model X Pert-Pro from PANALYTICAL, Netherlands. The test conditions are Cu target Kalpha light source, Ni filtering, tube point current of 40mA, tube voltage of 40kV and scanning speed of 0.2S-1。
Specific surface area of the sample by N2The adsorption-desorption experiment test analysis is carried out, the analytical instrument is AutosorbiQ Station 2 of Quanta chrome company, the test condition is that after pretreatment is carried out for 5 hours at 300 ℃, N is used2Is adsorbed by adsorbate at constant temperature of 77K.
Example 1
1) Preparation of carbon spheres
Taking glucose as a raw material, preparing 0.5mol/L glucose aqueous solution, transferring 68mL of the glucose solution to a 100mL hydrothermal kettle, and reacting for 6h at 190 ℃; naturally cooling the hydrothermal kettle to room temperature to obtain black or black brown suspension; transferring the suspension into a centrifugal tube, centrifuging for 8min at the rotating speed of 11000rpm/min, pouring out supernatant, and centrifuging and washing for 2 times by using deionized water and ethanol respectively to obtain black precipitate;
and drying the obtained precipitate in an oven at 60 ℃ for 6h to obtain carbon sphere particles.
2) Modifying a carbon sphere template
Diluting 68 wt% nitric acid to prepare a nitric acid solution with the concentration of 1 mol/L; and (3) adding 1g of the carbon spheres obtained in the step (1) into 100mL of nitric acid solution with the concentration of 1mol/L, standing for 24h, respectively washing and centrifuging for 3 times by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain the acid modified carbon spheres.
3) Preparation of precursor microspheres
Weighing 0.0429gZr (NO)3)4·5H2O and 0.0236gCa (NO)3)2·4H2And pouring the O into a beaker, adding 40mL of pure water, and stirring until the pure water is dissolved to obtain a metal salt mixed solution. Weighing 0.4g of the acid-modified carbon spheres prepared in the step 2), and addingAdding into the mixed solution of nitrate, and ultrasonically dispersing in an ultrasonic oscillator for 60min to obtain black brown suspension. And (3) stirring the black brown suspension at room temperature for 24 hours, and transferring the black brown suspension to a 60 ℃ oven for drying to obtain precursor microspheres.
4) Template for removing carbon balls
Placing the precursor microspheres obtained in the step 3) in a muffle furnace, roasting at 400 ℃ for 4h, then heating to 800 ℃ for 4h, calcining at the heating rate of 3 ℃/min, and naturally cooling to room temperature to obtain CaZrO3A material. This was designated as example-1.
Example 2
According to the technical scheme and the process flow, the precursor solution in the step 3) is changed into 0.0858g of Zr (NO)3)4·5H2O and 0.0472g Ca (NO)3)2·4H2O, the other steps are the same as example 1. The resulting product was named example-2.
Example 3
According to the technical scheme and the process flow, the precursor solution in the step 3) is changed into 0.2145g of Zr (NO)3)4·5H2O and 0.118g Ca (NO)3)2·4H2And O. The other steps are the same as in example 1. The resulting product was named example-3.
Example 4
According to the technical scheme and the process flow, the precursor solution in the step 3) is changed into 0.429g of Zr (NO)3)4·5H2O and 0.236g Ca (NO)3)2·4H2Other steps are the same as example 1. The resulting product was named example-4.
Example 5
According to the technical scheme and the process flow, the precursor solution in the step 3) is changed into 0.2145gZr (NO)3)4·5H2O and 0.1415g Sr (NO)3)2·4H2O, the other steps are the same as example 1. The resulting product was named example-5.
Example 6
According to the technical scheme and the process flow, the step 3) is preceded byThe precursor solution was changed to 0.2145gZr (NO)3)4·5H2O and 0.1305g Sr (NO)3)2·4H2O, the other steps are the same as example 1. The resulting product was named example-6.
Comparative example 1
Preparation of nano CaZrO by coprecipitation method3Comparison was made with the material of example-3. 3.631g ZrOCl2·8H2O and 1.4185g CaCl2·5H2O is put into a conical flask, 100mL of deionized water is added and mixed uniformly, and 1.928g (NH) is added into the mixture4)2C2O4·H2O、5mL NH3·H2O (25 wt%), 0.1g PEG20000 and 95mL deionized water, stirring for 1h, aging at 100 ℃ for 24h, washing and drying to obtain the precursor. Finally, presintering the precursor for 1h at 400 ℃ and roasting for 4h at 900 ℃ in air atmosphere to obtain nano CaZrO3The temperature rise rate is 3 ℃/min. The resulting product was named comparative example-1.
Comparative example 2
According to the technical scheme and the process flow, the aging temperature in the comparative example 1 is changed to 140 ℃, and other steps are the same as those in the comparative example 1. The resulting product was named comparative example-2.
Comparative example 3
According to the technical scheme and the process flow, the aging temperature in the comparative example 1 is changed to 180 ℃, and other steps are the same as the comparative example 1. The obtained product was named comparative example-3.
The method for performing morphology characterization test on the carbon spheres, the precursor microspheres and the final products provided by the embodiments and the comparative examples comprises the following steps:
obtaining the surface appearance of each substance through a scanning electron microscope; measuring the content of each substance by an X-ray energy spectrometer attached to the SEM; testing the crystal structure of each substance by X-ray diffraction; by N2The physical adsorption method tests the specific surface area of the perovskite material.
As can be seen from FIG. 1, glucose can be hydrothermally treated to obtain uniform carbon without adding any dispersant, surfactant, etcA ball. As can be seen from the scanning electron microscope image of the precursor microsphere in fig. 2 and the X-ray energy spectrum analysis result in table 1 (the EDS spectrogram result of the precursor microsphere in example 3 in table 1), the metal ions can be effectively attached to the acid-modified carbon spheres by using the acid-modified carbon spheres as the template. As can be seen from the scanning electron microscopy image of fig. 3, the material synthesized using the method of the present application has a loose structure. From N of FIG. 42The adsorption-desorption isotherms show that the adsorption-desorption curve of the prepared material is obviously changed and the pore structure is significantly increased compared with the material prepared by the coprecipitation method, and the specific surface area estimated according to the BET model is shown in Table 2, so that the specific surface area is significantly increased, and the increase factor is more than 1.7 times. The specific surface area of the products prepared in other examples is 20-100 m2Between/g. Meanwhile, the X-ray diffraction pattern of example 3 of FIG. 6 verifies that the product prepared by the method is a perovskite material. As can be seen from FIGS. 5 and 6, the products prepared in comparative examples 1 to 3 are all bulk materials and have irregular shapes.
Table 1 EDS spectra results of precursor microspheres
| Element(s) | Line type | Apparent concentration | k ratio | wt％ | wt％Sigma | Atomic percent |
| O | K line system | 8.34 | 0.02806 | 28.31 | 0.56 | 59.45 |
| Ca | K line system | 17.31 | 0.15463 | 30.10 | 0.40 | 25.23 |
| Zr | L-shaped wire system | 19.86 | 0.19856 | 41.59 | 0.55 | 15.32 |
| Total amount: | 100.00 | 100.00 |
TABLE 2 preparation of the product of example 3 and comparative examples 1 to 3N2Physical adsorption data
| Comparative example 1 | Comparative example-2 | Comparative example-3 | Example 3 | |
| Specific surface area (m)2/g) | 20.1 | 10.1 | 7.5 | 34.7 |
The regeneration efficiency of the products prepared in the above examples and comparative examples 1 to 3 in the process of regenerating activated carbon by catalytic wet oxidation was tested. The test procedure was as follows: 0.72g of saturated activated carbon was weighed out and mixed with 200mL of ultrapure water, and poured into an autoclave, and 0.2g of the product prepared in the above example and comparative example was added at the same time. And (3) screwing the reaction kettle, filling 2MPa of oxygen, starting a temperature controller to heat to 260 ℃ at a heating rate of 5 ℃/min when the pressure of the device is stable, and simultaneously starting a stirring switch to reach the rotation speed of 600rpm/min required by the experiment. When the temperature and the rotating speed reach preset values, the reaction kettle starts to work at constant temperature, and the regeneration reaction time is also counted by taking the temperature and the rotating speed as starting points. After the regeneration reaction is finished, after the high-pressure kettle is cooled to room temperature, the liquid in the kettle is discharged by pressure relief, the activated carbon is taken out, dried at 105 ℃ for 2 hours, taken out and weighed, and used for a regeneration efficiency evaluation experiment. Wherein the regeneration efficiency is evaluated by adding 50mL of 1000 mg/L m-cresol solution into a ground conical flask and then adding regenerated activated carbon. Placing the conical flask in a water bath constant temperature oscillator, oscillating at the room temperature at the rotating speed of 120rpm/min for 24h, measuring the final concentration of m-cresol by high performance liquid chromatography, and calculating the actual adsorption capacity of the activated carbon to the m-cresol, wherein the ratio of the actual adsorption capacity to the theoretical adsorption capacity is the regeneration efficiency.
The product of example 3 is exemplified. As can be seen from fig. 7, the regeneration efficiency of wet oxidation regeneration without adding a catalyst was only 48%. Compared with the materials prepared in comparative examples 1-3, the catalytic regeneration efficiency of the material obtained in example 3 is improved from 58%, 64% and 66% to 85%. Therefore, in the process of regenerating the activated carbon by the catalytic wet oxidation method, the material with large specific surface area is adopted to improve the regeneration efficiency.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The perovskite material is characterized in that the structural formula is ABO3Wherein A is selected from at least one of Ca, Sr and Ba, and B is selected from at least one of Zr, Ti and Hf;
the perovskite material has a porous structure.
2. The perovskite material of claim 1, wherein the perovskite material has a specific surface area of 20 to 100m2/g；
Preferably, the specific surface area of the perovskite material is 30-100 m2/g。
3. A method for producing a perovskite material as claimed in claim 1 or 2, characterized in that it comprises at least the following steps:
(1) carrying out reaction I on a mixed solution I consisting of a carbon source and water to obtain carbon nanospheres;
(2) carrying out a reaction II on a mixed solution II containing acid and the nano carbon spheres to obtain acid modified carbon spheres;
(3) carrying out a reaction III on a mixed solution III containing the acid modified carbon spheres, the metal source A and the metal source B to obtain precursor microspheres;
(4) and calcining the precursor microspheres to obtain the perovskite material.
4. The method according to claim 3, wherein the carbon source in the step (1) is at least one selected from glucose, fructose, sucrose and starch;
preferably, the concentration of the carbon source in the mixed solution I is 0.3-0.7 mol/L;
preferably, the specific conditions of the reaction I include:
the hydrothermal reaction temperature is 160-190 ℃;
the hydrothermal reaction time is 4-12 h.
5. The method according to claim 3, wherein the acid in the step (2) is at least one of nitric acid, hydrochloric acid, phosphoric acid, and sulfuric acid;
preferably, the content of acid in the mixed solution II is 0.5-6 mol/L;
preferably, the content of the carbon nanospheres in the mixed solution II is 2-10 g/L;
preferably, the solvent in the mixed solution II is water.
6. The process according to claim 3, wherein the specific conditions of the reaction II comprise:
the reaction temperature is 10-40 ℃;
the reaction time is 12-48 h.
7. The production method according to claim 3, wherein the A metal source in the step (3) is at least one of Ca nitrate, Sr nitrate, Ba nitrate;
preferably, the B metal source is at least one of Zr nitrate, Ti nitrate and Hf nitrate;
preferably, the molar ratio of the A metal source to the B metal source is 1:1 to 1.5, wherein the molar amount of the A metal source is calculated by the molar amount of the A metal, and the molar amount of the B metal source is calculated by the molar amount of the B metal;
preferably, the mass ratio of the acid-modified carbon spheres to the metal source is 0.9-50: 1, wherein the metal source is the sum of a metal source A and a metal source B;
preferably, the solvent in the mixed solution III is water;
preferably, the concentration of the A metal source in the mixed liquid III is 0.001-0.01 mol/L.
8. The method according to claim 3, wherein the specific conditions of reaction III include:
the reaction temperature is 20-40 ℃;
the reaction time is 6-24 h.
9. The preparation method according to claim 3, wherein the specific conditions of the calcination include: roasting for 2-6 h at 300-500 ℃, and then heating to 700-900 ℃ for 2-10 h.
10. Use of at least one of the perovskite material according to claim 1 or 2 and the perovskite material prepared by the preparation method according to any one of claims 3 to 9 in the regeneration of activated carbon by a catalytic wet oxidation method.
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