CN112755992A - Perovskite ceramic oxide with high specific surface area by flame method, and preparation method and application thereof - Google Patents
Perovskite ceramic oxide with high specific surface area by flame method, and preparation method and application thereof Download PDFInfo
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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
-
- 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
-
- B01J35/61—
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
A perovskite ceramic oxide material with Ca at the A site is prepared by a flame method by using metal nitrate, citric acid with the ratio of 1:1 and ethylene glycol as a complexing agent. The perovskite functional material manufactured by the invention has short burning duration of about 15-20 seconds, and generates a large amount of fluffy solid. The volume of the solid product is obviously expanded, the temperature is obviously reduced after the reaction, and the generated solid product is porous and has better dispersibility. The generation of various gas-phase products in the burning reaction process inhibits the growth of the grain diameter, and is beneficial to the formation of the nano powder with high specific surface area. Has good homogeneity, smaller particles and larger specific surface area.
Description
Technical Field
The invention belongs to the technical field of producing perovskite ceramic oxide by using a nanotechnology and a chemical method and the field of catalyst preparation, and particularly relates to a preparation method of perovskite ceramic oxide with high specific surface area by using a flame method.
Background
The perovskite type oxide contains rich oxygen defects, is a complete oxidation type catalytic material, and is widely applied to the fields of oxidation-reduction reaction catalysts, solid resistors, high-temperature heating materials, high-temperature solid fuel cells, chemical sensors and the like. Perovskite oxides are considered promising noble metal replacement catalysts in fuel cells due to their low cost, high hydrothermal stability, and resistance to poisoning. In recent years, doping has been carried out to improve the intrinsic activity of perovskite type oxides, but the low temperature oxidation activity is still lower than that of Pt/Pd catalysts, so research on such materials focuses on finding new substitute elements and improving preparation methods to further improve the electrical conductivity, increase the active sites and thus improve the activity thereof. The morphology, crystal structure, defects and chemical components of perovskite oxides are closely related to the preparation method and constituent elements thereof. Therefore, the rules and the change mechanism in the process of preparing the material need to be searched, a new preparation process is found, the existing process is improved, and the high and new technical material with excellent performance is prepared.
The preparation method has great influence on the structure and performance of the material, and the preparation of the perovskite type oxide mostly adopts a coprecipitation method, a sol-gel method, a high-temperature solid phase method and a hydrothermal synthesis method.
A coprecipitation method: and (3) dropwise adding a proper precipitator into the uniform solution in which different reaction raw materials are dissolved at a constant speed to obtain a precursor precipitate, washing, drying and calcining to obtain a reaction product. The advantages are that: can obtain nano powder material with uniform chemical components, and is easy to prepare nano powder material with small granularity and uniform distribution. Due to the non-uniform precipitation, the precipitates are easily aggregated together, and slight sintering occurs during calcination, thereby reducing the specific surface area of the catalyst.
Sol-gel method: dissolving reactants in liquid to form sol, aging, polymerizing to form gel, curing, and performing high-temperature treatment to obtain the required nano material such as nano particles. The advantages are that: the method has simple operation, the raw materials are dispersed into the solvent to realize uniform mixing at the molecular level, the synthesis temperature is low, the particle size of the prepared powder is small, and the like. The disadvantages are as follows: the time required by the whole process is longer; a large amount of gas and organic matters can escape from the gel in the drying process, and the product has large volume shrinkage and is not beneficial to industrial production.
High-temperature solid phase method: the solid raw materials are uniformly mixed according to the stoichiometric ratio, ground and calcined at high temperature for multiple times to obtain a single-phase product. Has the advantages of low cost, simple process, high yield and the like. The disadvantages are as follows: such as high reaction temperature, slow reaction rate, uneven powder product, etc.
Hydrothermal synthesis method: the hydrothermal method is a preparation method of recrystallization after dissolving raw materials by taking water or organic liquid as a solvent in a sealed pressure container, and has the advantages that: the sample preparation process can prevent the sample from being polluted, the evaporation loss and the pollution of toxic and harmful substances to the environment.
Bell R J, Millar G J, Drennan J. infiluence of synthetic routes on the catalytic properties of La1xSrxMnO 3J. Solid State Ionics, 2000, 131(3-4):211-220. pure phase CaMnO3 prepared by high temperature Solid phase synthesis method was found to have ZT value of only 0.01 at 375K. The document Sotelo A, Constantinescu G, Rasekh S, et al, Improvement of thermal properties of Ca3Co4O9 using soft chemistry synthesis methods [ J ]. Journal of the European Ceramic Society, 2012, 32(10):2415-2422. compared with the solid phase synthesis method, the Ca3Co4O9 product synthesized by the sol-gel method has better thermoelectric properties. The PF value is 2 times higher than that of the traditional solid phase synthesis method. The perovskite oxide catalyst prepared by the solid-phase synthesis method has high roasting temperature, low crystallinity and large and uncontrollable particle size of the product. Solvothermal synthesis and Catalysis of mixed oxides with a peroxide-like structure [ J ]. Catalysis Today, 2015, 257:26-34. hydrothermal synthesis requires conditions of high temperature and high pressure and a special sealed pressure vessel. Compared with the solid phase method, the sol-gel method has the advantages that in the whole process, the raw materials are uniformly mixed at the molecular level, atoms are easier to enter lattice position points through rearrangement or short-range diffusion, and therefore CaMnO3 powder with high purity, uniform particle size and higher activity is easier to obtain. And the preparation time is short, the parameters are controllable, and the method is simple and convenient. But requires a long drying time. When A is Ca-type perovskite oxide powder, the flame method is used for preparing ABO3, the time is shorter, the equipment is simple, and the prepared material has larger specific surface area, so that more surface active sites are increased, and more oxygen vacancies are obtained, wherein the oxygen vacancies are important conditions for realizing the semiconductor, and the control of the oxygen vacancies is an important factor for preparing perovskite semiconductor functional ceramic elements.
In addition, in the prior art, for example, Chinese patent application (application No. CN201710039086, publication No. CN 106810254A) discloses a method for synthesizing a double perovskite Sr2MnWO6 ceramic material, wherein MnO and WO3 are mixed firstly, the reaction activity of the MnO and the WO3 is activated by pre-sintering, then the other raw material SrCO3 with the metering ratio is weighed, and the raw material is ground for 1-3 hours to be tableted and sintered to finally prepare the double perovskite Sr2MnWO6 ceramic material. Chinese patent application (application number: CN201911033940, publication number: CN 110885249A) discloses a barium-based perovskite ceramic material, a preparation method and application thereof, wherein the preparation method comprises the steps of burdening raw materials of BaCO3, TiO2, ZrO2 and GeO2 according to the stoichiometric molar ratio of Ba (Zr0.2Ti0.8-xGex) O3, pre-treating and pre-burning, wherein x is 0.001-0.00175; mixing the pre-sintered raw materials with polyvinyl alcohol, grinding, drying and sieving; preparing the sieved material into a green body; and sintering the green body. Chinese patent application (application No. CN200810156129, publication No. CN 101359739A) discloses a solid oxide fuel cell cathode material and a preparation method thereof, wherein the chemical formula of the material is MxA1-xM’yB1-yO3-δ. The material is prepared by an EDTA-citric acid combined complexing method or a glycine combustion method. The cathode material can be coated on the surface of electrolyte by screen printing, spraying, dip coating or tape casting, and then baked at high temperature to obtain the cathode catalyst layer. When the catalytic layer is in a working state, namely when negative current passes through the electrode, the noble metal oxide obtains electrons to perform reduction reaction, and the electrons come out from the crystal lattice of the perovskite or perovskite-like ceramic material and are enriched on the surface of the material to form the noble metal-ceramic composite cathode. The noble metal can be heavy again when a positive current passes through the electrodeNew oxidation into the ceramic oxide lattice. Chinese patent application (application No. CN201510478036, publication No. CN 105080359A) discloses a preparation method of a ceramic hollow fiber oxygen permeable membrane bundle, which adopts a technical route of ceramic hollow fiber membrane preforming and bundling sintering: (1) preparing a ceramic hollow fiber membrane precursor by using a dry-wet spinning method, and sintering at a high temperature to obtain an oxygen permeable membrane with a fixed hollow fiber shape and certain strength; (2) preparing a polymer sol containing a perovskite mixed conductor ceramic powder material, bonding a plurality of preformed ceramic hollow fiber membranes into a whole through a mold, and bundling, curing and molding; (3) and (3) sintering the collected ceramic hollow fiber membrane at high temperature by adopting temperature programming, and finally preparing the ceramic hollow fiber oxygen permeable membrane bundle. The prepared ceramic hollow fiber membrane bundle has high strength, is convenient to assemble into a ceramic oxygen permeation membrane component, and has oxygen permeation capacity obviously higher than that of a single hollow fiber membrane.
Although the prior art relates to the preparation method and application of the perovskite ceramic material, the perovskite ceramic material can not meet the application of industrial production through experimental analysis, the combustion duration of the adopted perovskite functional material is long, fluffy and large-amount solids can not be generated, the temperature is slowly reduced after reaction, and the generated solid product has few pores and poor dispersibility.
Disclosure of Invention
The invention provides a preparation method of a flame method perovskite catalyst with high specific surface area, which solves the defects in the prior art.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
a preparation method of a flame-process perovskite ceramic oxide with high specific surface area is characterized by comprising the following steps:
s1, weighing soluble nitrates Ca (NO 3) 2.4H 2O and Mn (NO 3) 2 in a beaker according to a stoichiometric ratio, adding a proper amount of deionized water, stirring until the nitrates are completely dissolved to obtain a clear solution, weighing citric acid in a certain proportion to metal salt ions, adding the citric acid into the solution, simultaneously dropwise adding a proper amount of ethylene glycol as a complexing agent at a constant speed, stirring uniformly, preparing a polymer precursor solution, and preventing the metal ions from aggregating. The polymer precursor process ensures the stability of metal cations in the precursor both chemically and physically.
And S2, heating and stirring the mixed clear solution on a magnetic stirrer, and continuously magnetically stirring the solution at 90 ℃ to obtain a viscous liquid to obtain clear and viscous sol.
S3, placing the prepared viscous sol on an electric heating plate for uniform heating until the ignition temperature is about 350-400 ℃, and the sol is violently combusted, and the volume of the catalyst rapidly expands. The duration is about 20 s.
S4, the sample that had completely burned was taken out and ground in an agate mortar to reduce the volume.
S5, placing the ground powder sample on a dry pot, and feeding the powder sample into a muffle furnace to be burned for 8 hours at 800 ℃.
And S6, taking out the fired sample, and burning the sample in a high-temperature muffle furnace at 1300 ℃ for 5 hours. Finally obtaining the required sample.
The invention also discloses a perovskite ceramic oxide with high specific surface area by a flame method, which is characterized in that: the perovskite ceramic oxide material with Ca at the A site prepared by a flame method by using metal nitrate, citric acid with a ratio of 1:1 and ethylene glycol as a complexing agent has the advantages of high specific surface area, small particle size, good homogeneity, simple preparation process and conditions and short preparation time. The ceramic material prepared by the method can be used as a high-temperature catalyst for oxidation-reduction reaction, a thermoelectric material, an electrode material and the like.
Has the advantages that:
1. the invention realizes the preparation of the perovskite catalyst with Ca at the A site, has simple preparation method, does not need high pressure condition and has lower roasting temperature.
2. The perovskite functional material manufactured by the invention has short burning duration of about 15-20 seconds, and generates a large amount of fluffy solid. The volume of the solid product is obviously expanded, the temperature is obviously reduced after the reaction, and the generated solid product is porous and has better dispersibility. The generation of various gas-phase products in the burning reaction process inhibits the growth of the grain diameter, and is beneficial to the formation of the nano powder with high specific surface area. Has good homogeneity, smaller particles and larger specific surface area.
3. The invention can save long drying time, has short reaction time, and can be directly used for preparing the catalyst in the oxidation-reduction reaction and the perovskite oxide thermoelectric material.
4. The flame method can provide enough heat for the system, ensure to form stable complex with metal ions, increase the solubility of the complex and prevent the selective precipitation of the metal ions in the water removal process.
5. The material prepared by the invention can be used for preparing catalysts for redox reactions such as methane reforming and the like, and can also be used for preparing anode materials of zinc-air batteries, electrode materials of various solid fuel cells, thermoelectric materials, automobile/diesel exhaust emission treatment and the like.
Drawings
FIG. 1: example 1 the relative density profiles of samples of high specific surface area perovskite ceramic oxides at different sintering temperatures using a flame method.
FIG. 2: the X-ray diffraction patterns of the perovskite ceramic oxide with high specific surface area by adopting a flame method at different sintering temperatures are adopted.
FIG. 3: example 1 SEM photograph of perovskite type oxide with Ca at a-site prepared by flame method;
FIG. 4: example 2 SEM photograph of perovskite type oxide with Ca at a-site prepared by gel sol method.
FIG. 5: example 3 SEM photograph of perovskite type oxide with Ca at a-site prepared by high temperature solid phase method.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Compared with the alloy, the transition metal oxide CaMnO3 thermoelectric material has the advantages of simple preparation process, low raw material toxicity, high self-melting point, stability in air and the like, but the carrier concentration is low, so that the material can be subjected to low-dimensional preparation by adopting a flame method, the structure, the energy band structure, the carrier concentration, the mobility and the like of a crystal are changed, and the performance of the functional material is improved.
The crystal structure, morphology, conductivity, and oxygen vacancies of the perovskite oxide all affect the catalytic performance of the perovskite oxide. The construction of the ordered micro/nano structure can greatly increase the specific surface area of the catalyst, increase the exposure of surface active sites, promote gas diffusion, improve reaction quality transmission and the like. If the preparation time is too long, the specific surface area is reduced and the catalytic ability is weakened due to too high temperature. How to increase the specific surface area and pore size distribution of the perovskite type oxide, generate more metal centers and have the migration capability of oxygen is the bottleneck of the catalyst. Therefore, a suitable preparation process is of great importance.
The main criteria for evaluating the quality of the prepared perovskite oxide powder are as follows:
1. controllability of powder particle size
2. Stability of the crystalline phase
3. Consistency of geometry
4. Degree of agglomeration of the powder.
Based on the above standards for preparing perovskite oxides, the method for synthesizing perovskite oxides by flame method mixes and stirs raw materials to obtain uniform catalyst precursor solution, then the whole material is uniformly heated until the whole combustion reaction is spontaneously formed in volume, and finally the perovskite oxide is obtained by roasting under a certain temperature condition. Compared with a hydrothermal synthesis method, the method has the advantages of simple reaction equipment, no need of high-pressure conditions, lower roasting temperature compared with the existing solid phase synthesis method, faster temperature rise in the synthesis process, no need of long drying time compared with a sol-gel method, and short reaction time. The product prepared by the method has good homogeneity, smaller particle size and higher conductivity.
The invention adopts a flame method to prepare the perovskite type oxide with Ca at the A site, and prepares the perovskite type catalyst with Ca at the A site by adjusting the concentration and the proportion of the precursor, controlling the time for forming gel of the solution, controlling the temperature for heating the gel by an electric heating plate, collecting the time for collecting a sample, grinding the sample and the like. Compared with a hydrothermal synthesis method, the method has the advantages of simple reaction equipment, no need of high-pressure conditions, lower roasting temperature compared with the existing solid phase synthesis method, faster temperature rise in the synthesis process, no need of long drying time compared with a sol-gel method, and short reaction time. The product prepared by the method has good homogeneity, smaller particle size and higher conductivity. The catalyst prepared by the method can improve the stability of the catalyst, is simple to operate and can be produced in batches. The preparation process is easy to control, the preparation time is short, and the preparation conditions are simple.
Example 1
Example 1.1
A preparation method of a perovskite ceramic oxide with high specific surface area by adopting a flame method is characterized by comprising the following steps:
s1, respectively weighing 1g of soluble nitrates Ca (NO 3) 2.4H 2O and Mn (NO 3) 2 in a beaker according to a stoichiometric ratio, adding a proper amount of 50ml of deionized water, stirring until the nitrates are completely dissolved to obtain a clear solution, weighing citric acid which has a ratio of 1:1 with metal salt ions, adding the citric acid into the solution, simultaneously dropwise adding a proper amount of glycol as a complexing agent at a constant speed, stirring uniformly, preparing a polymer precursor solution, and preventing the metal ions from aggregating. The polymer precursor method ensures the stability of metal cations in the precursor from two aspects of chemistry and physics;
and S2, heating and stirring the mixed clear solution on a magnetic stirrer, and continuously magnetically stirring the solution at 90 ℃ to obtain a viscous liquid to obtain clear and viscous sol.
S3, placing the prepared viscous sol on an electric heating plate for uniform heating until the ignition temperature is about 350-400 ℃, and the sol is violently combusted, and the volume of the catalyst rapidly expands. The duration is about 20 s.
S4, the sample that had completely burned was taken out and ground in an agate mortar to reduce the volume.
S5, placing the ground powder sample on a dry pot, and feeding the powder sample into a muffle furnace to be burned for 8 hours at 800 ℃.
And S6, taking out the fired sample, and burning the sample in a high-temperature muffle furnace at 1300 ℃ for 5 hours. Finally obtaining the required sample.
The perovskite oxide functional material with Ca at the A site prepared in the embodiment has the following performance parameters:
the sintering temperature is 1300 ℃, the relative density of the sample is 95.19 percent, the weight loss of the sample is 3.70474 percent through thermogravimetric analysis, and the specific surface area is 34 percentXRD diffraction pattern 2.
Example 1.2
A preparation method of a perovskite ceramic oxide with high specific surface area by adopting a flame method is characterized by comprising the following steps:
s1, respectively weighing 1g of soluble nitrates Ca (NO 3) 2.4H 2O and Mn (NO 3) 2 in a beaker according to a stoichiometric ratio, adding a proper amount of 50ml of deionized water, stirring until the nitrates are completely dissolved to obtain a clear solution, weighing citric acid which has a ratio of 1:1 with metal salt ions, adding the citric acid into the solution, simultaneously dropwise adding a proper amount of glycol as a complexing agent at a constant speed, stirring uniformly, preparing a polymer precursor solution, and preventing the metal ions from aggregating. The polymer precursor method ensures the stability of metal cations in the precursor from two aspects of chemistry and physics;
and S2, heating and stirring the mixed clear solution on a magnetic stirrer, and continuously magnetically stirring the solution at 90 ℃ to obtain a viscous liquid to obtain clear and viscous sol.
S3, placing the prepared viscous sol on an electric heating plate for uniform heating until the ignition temperature is about 350-400 ℃, and the sol is violently combusted, and the volume of the catalyst rapidly expands. The duration is about 20 s.
S4, the sample that had completely burned was taken out and ground in an agate mortar to reduce the volume.
S5, placing the ground powder sample on a dry pot, and feeding the powder sample into a muffle furnace to be burned for 8 hours at 800 ℃.
And S6, taking out the fired sample, and burning the sample in a high-temperature muffle furnace at 900 ℃ for 5 hours. Finally obtaining the required sample.
The sintering temperature is 900 ℃, the relative density of the sample is 76.37%, the weight loss of the sample is 3.2746% through thermogravimetric analysis, and the specific surface area is 30.2XRD diffraction pattern 2.
Example 1.3
A preparation method of a perovskite ceramic oxide with high specific surface area by adopting a flame method is characterized by comprising the following steps:
s1, respectively weighing 1g of soluble nitrates Ca (NO 3) 2.4H 2O and Mn (NO 3) 2 in a beaker according to a stoichiometric ratio, adding a proper amount of 50ml of deionized water, stirring until the nitrates are completely dissolved to obtain a clear solution, weighing citric acid which has a ratio of 1:1 with metal salt ions, adding the citric acid into the solution, simultaneously dropwise adding a proper amount of glycol as a complexing agent at a constant speed, stirring uniformly, preparing a polymer precursor solution, and preventing the metal ions from aggregating. The polymer precursor method ensures the stability of metal cations in the precursor from two aspects of chemistry and physics;
and S2, heating and stirring the mixed clear solution on a magnetic stirrer, and continuously magnetically stirring the solution at 90 ℃ to obtain a viscous liquid to obtain clear and viscous sol.
S3, placing the prepared viscous sol on an electric heating plate for uniform heating until the ignition temperature is about 350-400 ℃, and the sol is violently combusted, and the volume of the catalyst rapidly expands. The duration is about 20 s.
S4, the sample that had completely burned was taken out and ground in an agate mortar to reduce the volume.
S5, placing the ground powder sample on a dry pot, and feeding the powder sample into a muffle furnace to be burned for 8 hours at 800 ℃.
And S6, taking out the fired sample, and burning the sample in a high-temperature muffle furnace for 5 hours at 1000 ℃. Finally obtaining the required sample.
The sintering temperature is 1000 ℃, the relative density of the sample is 84.46%, and the weight loss of the sample is 2.52605 by thermogravimetric analysis% specific surface area of 31The XRD diffractogram is shown in FIG. 2.
Example 1.4
A preparation method of a perovskite ceramic oxide with high specific surface area by adopting a flame method is characterized by comprising the following steps:
s1, respectively weighing 1g of soluble nitrates Ca (NO 3) 2.4H 2O and Mn (NO 3) 2 in a beaker according to a stoichiometric ratio, adding a proper amount of 50ml of deionized water, stirring until the nitrates are completely dissolved to obtain a clear solution, weighing citric acid which has a ratio of 1:1 with metal salt ions, adding the citric acid into the solution, simultaneously dropwise adding a proper amount of glycol as a complexing agent at a constant speed, stirring uniformly, preparing a polymer precursor solution, and preventing the metal ions from aggregating. The polymer precursor method ensures the stability of metal cations in the precursor from two aspects of chemistry and physics;
and S2, heating and stirring the mixed clear solution on a magnetic stirrer, and continuously magnetically stirring the solution at 90 ℃ to obtain a viscous liquid to obtain clear and viscous sol.
S3, placing the prepared viscous sol on an electric heating plate for uniform heating until the ignition temperature is about 350-400 ℃, and the sol is violently combusted, and the volume of the catalyst rapidly expands. The duration is about 20 s.
S4, the sample that had completely burned was taken out and ground in an agate mortar to reduce the volume.
S5, placing the ground powder sample on a dry pot, and feeding the powder sample into a muffle furnace to be burned for 8 hours at 800 ℃.
S6, taking out the fired sample, and burning the sample in a high-temperature muffle furnace at 1100 ℃ for 5 hours. Finally obtaining the required sample.
The sintering temperature is 1100 ℃, the relative density of the sample is 93.40%, the weight loss of the sample after thermogravimetric analysis is 2.63498%, and the specific surface area is 29.46%The XRD diffractogram is shown in FIG. 2.
Example 1.5
A preparation method of a perovskite ceramic oxide with high specific surface area by adopting a flame method is characterized by comprising the following steps:
s1, respectively weighing 1g of soluble nitrates Ca (NO 3) 2.4H 2O and Mn (NO 3) 2 in a beaker according to a stoichiometric ratio, adding a proper amount of 50ml of deionized water, stirring until the nitrates are completely dissolved to obtain a clear solution, weighing citric acid which has a ratio of 1:1 with metal salt ions, adding the citric acid into the solution, simultaneously dropwise adding a proper amount of glycol as a complexing agent at a constant speed, stirring uniformly, preparing a polymer precursor solution, and preventing the metal ions from aggregating. The polymer precursor method ensures the stability of metal cations in the precursor from two aspects of chemistry and physics;
and S2, heating and stirring the mixed clear solution on a magnetic stirrer, and continuously magnetically stirring the solution at 90 ℃ to obtain a viscous liquid to obtain clear and viscous sol.
S3, placing the prepared viscous sol on an electric heating plate for uniform heating until the ignition temperature is about 350-400 ℃, and the sol is violently combusted, and the volume of the catalyst rapidly expands. The duration is about 20 s.
S4, the sample that had completely burned was taken out and ground in an agate mortar to reduce the volume.
S5, placing the ground powder sample on a dry pot, and feeding the powder sample into a muffle furnace to be burned for 8 hours at 800 ℃.
And S6, taking out the fired sample, and burning the sample in a high-temperature muffle furnace at 1200 ℃ for 5 hours. Finally obtaining the required sample.
The sintering temperature is 1200 ℃, the relative density of the sample is 94.26%, the weight loss of the sample after thermogravimetric analysis is 2.74261%, and the specific surface area is 32.16The XRD diffractogram is shown in FIG. 2.
Through the analysis, the perovskite type oxide prepared by the flame method has higher relative density of a sample at the sintering temperature of 1300 ℃, and the thermogravimetric analysis shows that the obtained oxygen vacancy is higher and the specific surface area is higher.
Example 2
The preparation method for preparing the perovskite ceramic oxide by adopting the gel sol method comprises the following steps: s1, respectively weighing 1g of soluble nitrates Ca (NO 3) 2.4H 2O and Mn (NO 3) 2 in a beaker according to a stoichiometric ratio, adding a proper amount of 50ml of deionized water, stirring until the nitrates are completely dissolved to obtain a clear solution, weighing citric acid which is 1:1 in proportion to metal salt ions, adding the citric acid into the solution, simultaneously dropwise adding a proper amount of glycol as a complexing agent at a constant speed, stirring uniformly, and preparing a polymer precursor solution.
And S2, continuously stirring the mixed solution in warm water at 85 ℃ in a water bath to form a colloid.
S3, and drying the colloid in a drying oven at 90 ℃ for 48 hours to obtain dry gel.
S4, the xerogel is calcined in a muffle furnace at 800 ℃ for 5 hours.
S5, taking out the fired sample, grinding and calcining at 1300 ℃ in a high-temperature muffle furnace for 20 hours. Finally obtaining the required sample.
Example 2 a perovskite oxide in which the a site is Ca, which is prepared by a gel sol method, is shown in fig. 4 as an SEM photograph thereof.
Example 3
The preparation method of the perovskite ceramic oxide by adopting a high-temperature solid phase method comprises the following steps:
s1, weighing 1gde CaCO3(99%) and MnO2 (98%) as raw materials according to the stoichiometric ratio of 1:1, wherein the balance model is FA1004B, and the precision can be 0.1 mg.
And S2, accurately weighing, placing the reactant in an agate mortar, adding a small amount of absolute ethyl alcohol, and grinding for more than 4 hours.
S3, naturally drying the sample until the ethanol is volatilized, calcining the sample in a muffle furnace at 800 ℃ for 24 hours,
s4, carrying out secondary calcination on the calcined sample at 1150 ℃ for 36 hours to finally obtain a gray black CaMnO3 sample.
SEM photograph of Ca-site perovskite type oxide prepared by high temperature solid phase method of this example is shown in FIG. 5.
From the above-described embodiments and the drawings thereof, the skilled person will conclude that:
by comparing perovskite oxides prepared at different sintering temperatures by a flame method, the sintering temperature is optimal at 1300 ℃, the diffraction peak of the product is strongest, and the result shows that the crystallization degree of a sample is best. And the relative density of the sample is obviously increased along with the increase of the sintering temperature, and reaches 95.19 percent when the sintering temperature is 1300 ℃.
The preparation method comprises the following steps: compared with a flame method, a sol-gel method and a high-temperature solid phase method, the CaMnO3 type perovskite oxide prepared by the flame burning method does not need natural drying time, so that the time for preparing the material is greatly shortened.
It can be seen from the scanning electron micrograph of the sample that the samples from examples 2 and 3 have a large average particle size, few oxygen vacancies, a small density, and no anisotropy in orientation. While the sample prepared in example 1 has a larger specific surface area and a theoretical density of 4.58g/cm3 of CaMnO3, and has better homogeneity and smaller granularity. While the density obtained by the high temperature solid phase method is only 3.99 g/cm 3. The relative density was only 87%, while the density prepared by the sol-gel method was only 4.18 g/cm 3. The relative density is only 91.26%. The density of the flame-prepared material can reach 4.36 g/cm3, and the relative density is 95.19%.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A flame-processed perovskite ceramic oxide having a high specific surface area, characterized in that: the perovskite ceramic oxide material with Ca at the A site is prepared by a flame method by using metal nitrate, citric acid with the ratio of 1:1 and ethylene glycol as a complexing agent.
2. A method for preparing a flame-processed high specific surface area perovskite ceramic oxide, comprising the flame-processed high specific surface area perovskite ceramic oxide as claimed in claim 1, characterized in that the preparation method comprises the steps of:
s1, weighing soluble nitrates Ca (NO 3) 2.4H 2O and Mn (NO 3) 2 in a beaker according to a stoichiometric ratio, adding a proper amount of deionized water, stirring until the nitrates are completely dissolved to obtain a clear solution, weighing citric acid in a certain proportion to metal salt ions, adding the citric acid into the solution, simultaneously dropwise adding a proper amount of glycol as a complexing agent at a constant speed, stirring uniformly, preparing a polymer precursor solution, and preventing the metal ions from aggregating; the polymer precursor method ensures the stability of metal cations in the precursor from two aspects of chemistry and physics;
s2, placing the mixed clear solution on a magnetic stirrer, and heating and stirring to obtain sol;
s3, uniformly heating the prepared viscous sol on an electric heating plate;
s4, taking out the completely combusted sample, and grinding the sample in an agate mortar;
s5, placing the ground powder sample on a dry pot, and feeding the sample into a muffle furnace for firing;
and S6, taking out the fired sample, and burning the sample in a high-temperature muffle furnace for a plurality of hours at a certain temperature.
3. The method for preparing a high specific surface area perovskite ceramic oxide by flame method according to claim 2, characterized in that: the S2 further includes: heating to 90 ℃, and continuously magnetically stirring to obtain a viscous liquid to obtain clear and viscous sol.
4. The process for preparing a high specific surface area perovskite ceramic oxide by flame method as claimed in claim, wherein: the S3 further includes: the sol is intensively combusted when the uniform heating is carried out until the ignition temperature is about 350 ℃ and 400 ℃, and the volume of the catalyst is sharply expanded for about 20 s.
5. The process for preparing a high specific surface area perovskite ceramic oxide by flame method as claimed in claim, wherein: the S5 further includes: and (4) putting the mixture into a muffle furnace to be sintered for 8 hours at 800 ℃.
6. The process for preparing a high specific surface area perovskite ceramic oxide by flame method as claimed in claim, wherein: the S6 further includes: the certain temperature is set to 900 to 1300 degrees.
7. The method for preparing a high specific surface area perovskite ceramic oxide by flame method according to claim 6, characterized in that: the number of hours was set to 5 hours.
8. A catalyst for methane reforming redox reactions characterized by: comprising the perovskite type ceramic oxide prepared by the method for preparing a high specific surface area perovskite type ceramic oxide by flame method as claimed in any one of claims 1 to 7 as a catalyst.
9. A battery positive electrode material characterized in that: comprising the perovskite type ceramic oxide prepared by the preparation method of the high specific surface area perovskite type ceramic oxide by the flame method as claimed in any one of claims 1 to 7 as a battery positive electrode material.
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---|---|---|---|---|
CN115117468A (en) * | 2022-07-13 | 2022-09-27 | 华北电力大学 | Birnessite type delta-MnO for improving zinc electricity of water system 2 Electrolyte with positive polarity and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101684043A (en) * | 2009-08-28 | 2010-03-31 | 陈立华 | Novel perovskite manganese-base oxide material and preparation method thereof |
US20120282394A1 (en) * | 2009-12-28 | 2012-11-08 | Posco | Composite Ceramic Material and Method for Manufacturing the Same |
CN103372447A (en) * | 2012-04-26 | 2013-10-30 | 北京化工大学 | High-specific-surface-area perovskite catalyst LaCo0.9Mg0.1O3 and preparation method thereof |
CN111994959A (en) * | 2020-07-17 | 2020-11-27 | 中山大学 | CaMnO3Perovskite material and preparation method and application thereof |
-
2021
- 2021-01-08 CN CN202110024502.8A patent/CN112755992A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101684043A (en) * | 2009-08-28 | 2010-03-31 | 陈立华 | Novel perovskite manganese-base oxide material and preparation method thereof |
US20120282394A1 (en) * | 2009-12-28 | 2012-11-08 | Posco | Composite Ceramic Material and Method for Manufacturing the Same |
CN103372447A (en) * | 2012-04-26 | 2013-10-30 | 北京化工大学 | High-specific-surface-area perovskite catalyst LaCo0.9Mg0.1O3 and preparation method thereof |
CN111994959A (en) * | 2020-07-17 | 2020-11-27 | 中山大学 | CaMnO3Perovskite material and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
HIDEKI TAGUCHI ET AL.: "Methane Oxidation on Perovskite-Type Ca(Mn1-xTix)O3-δ", 《J. AM. CERAM. SOC.》 * |
JELENA MACAN ET AL.: "Soft chemistry synthesis of CaMnO3 powders and films", 《CERAMICS INTERNATIONAL》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115117468A (en) * | 2022-07-13 | 2022-09-27 | 华北电力大学 | Birnessite type delta-MnO for improving zinc electricity of water system 2 Electrolyte with positive polarity and preparation method thereof |
CN115117468B (en) * | 2022-07-13 | 2024-02-13 | 华北电力大学 | Lifting water system zinc-electricity Birnesite delta-MnO 2 Electrolyte with positive electrode performance and preparation method thereof |
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