CN110563462A - B-site six-element high-entropy novel perovskite type high-entropy oxide material and preparation method thereof - Google Patents
B-site six-element high-entropy novel perovskite type high-entropy oxide material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a novel B-site hexabasic high-entropy perovskite type high-entropy oxide material and a preparation method thereof, relating to the technical field of high-entropy oxide materials and having a chemical formula of RE (Al)1/6Cr1/6Fe1/6Mn1/ 6M1/6N1/6)O3Wherein RE is rare earth cation La3+、Pr3+、Nd3+、Sm3+、Gd3+And Y3+M and N are divalent cations Co2+、Ni2+、Mg2+and Zn2+Any two of them. The perovskite type high-entropy oxide nanocrystalline powder prepared by adopting a solution combustion method has high specific surface area andThe porous structure, the uniform chemical composition and the microstructure are convenient for regulating and controlling the microstructure, and finally the performance can be regulated and controlled as required.
Description
Technical Field
The invention relates to the technical field of high-entropy oxide materials, in particular to a novel B-site hexabasic high-entropy perovskite type high-entropy oxide material and a preparation method thereof.
Background
The High-entropy oxide (HEOs) breaks through the design concept of the traditional doped oxide, expands the design concept of the High-entropy alloy to a novel ceramic material developed in the field of Oxides, is also called as entropy stable oxide, is composed of five or more than five Oxides in an equimolar or nearly equimolar ratio, and has a configuration entropy more than or equal to 1.61R. On one hand, the high-entropy oxide system is easy to form simple rock salt type, fluorite type, spinel type or perovskite type solid solution structures due to high configuration entropy; on the other hand, since the main elements tend to be disorganized, i.e., their chemical compositions are in a disordered state, various properties are caused to be different from those of the conventional doped oxide. Since HEOs represent a collective characteristic due to multiple principal elements, they have attracted the interest of broad researchers due to their unique properties, such as extremely high thermal stability, unique magnetic properties, efficient lithium ion storage properties, huge dielectric properties, and excellent catalytic properties.
Perovskite type oxide with molecular formula ABO3Wherein, the A site cation is in a 12-coordination structure and is positioned at 12 vertex positions of the cubic unit cell, the B site cation is in a 6-coordination structure and is positioned at a body center position of the cubic unit cell, and the O ion is positioned at 6 face center positions. Because the perovskite oxide has diverse components and unique crystal structure, the perovskite oxide has certain superiority in the aspects of thermal stability, chemical stability and structural stability, and particularly the nano perovskite oxide is widely used as catalytic materials (photocatalysis, chemical catalysis, electrochemical catalysis and the like), solid oxide fuel cell cathode materials, microwave dielectric ceramic materials, piezoelectric ceramic materials and the like. 12 kinds of rare earth cations (RareEar) with A sites are prepared by Sarkar and the like in 2018 and adopting spray pyrolysis methodth，RE，Gd3+、La3+、Nd3+、Sm3+And Y3+) And the B site is a Transition Metal cation (TM, Co)2+、Cr3+、Fe3+、Mn2+And Ni2+) The oxide powder material of (1). Research shows that only 6 systems form a single perovskite type structure, namely A-site high-entropy (Gd)0.2La0.2Nd0.2Sm0.2Y0.2)CoO3B-site high entropy Gd (Co)0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3、La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3And Nd (Co)0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3And position A, B are both high entropy (Gd)0.2La0.2Nd0.2Sm0.2Y0.2)(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3High-entropy oxide powder materials (A.Sarkar, R.Djenadic, D.Wang, C.Hein, R.Kautenburg, O.Clemens, H.Hahn, Rare earth and distribution metal based entry stable perovskite types oxides, J.Eur.Ceram.Soc., 38(2018) 2318-2327.). Then Jiang et al prepare Ba (Zr) by mechanical ball milling and solid phase sintering method0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3And a series of perovskite type high-entropy oxide bulk materials with high entropy at B position (S.Jiang, T.Hu, J.Gild, N.Zhou, J.Nie, M.Qin, T.Harrington, K.Vecchio, J.Luo, Anewclass of high-entropy oxides, script Mater., 142(2018) 116-120). Sharma et al prepared Ba (Zr) using pulsed laser deposition0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3perovskite-type high-entropy oxide thin-film materials (y.sharma, b.l.musico, x.gao, c.hua, a.f.may, a.herklotz, a.rastogi, d.mandrus, j.yan, h.n.lee, m.f.chisholm, v.keppens, t.z.ward, Single-crystal high-entropy oxide epitaxial films, phys.rev.mater., 2(2018) 060404-060406.). Chinese patents CN 109650876 andCN 109607615 respectively prepares (La) with high entropy at A position by adopting a solid phase sintering method0.2Li0.2Ba0.2Sr0.2Ca0.2)TiO3And Ba (Zr) with high entropy at B position1/6Sn1/6Ti1/6Hf1/6Nb1/6)O3A perovskite-type high entropy oxide material.
In order to further expand the perovskite type high-entropy oxide and meet some special use requirements. The invention designs a novel perovskite type high-entropy oxide material with rare earth at A site and hexabasic high-entropy at B site for the first time. At present, no report related to the perovskite type high-entropy oxide, especially perovskite type nanocrystalline powder, is searched.
disclosure of Invention
Technical problem to be solved
the first aspect of the invention provides a perovskite type high-entropy oxide material with a rare earth at the A site and a hexabasic high-entropy at the B site; the invention also discloses a preparation method which is convenient to operate, strong in practicability and convenient to popularize, namely a solution combustion method, and the high-entropy oxide nanocrystalline powder material with high specific surface area and porous structure is obtained.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a B-position hexabasic high-entropy perovskite type high-entropy oxide material with a chemical formula of RE (Al)1/6Cr1/6Fe1/ 6Mn1/6M1/6N1/6)O3Wherein RE is rare earth cation La3+、Pr3+、Nd3+、Sm3+、Gd3+And Y3+M and N are divalent cations Co2+、Ni2+、Mg2+And Zn2+Any two of them.
The preparation method of the B-site hexabasic high-entropy perovskite type high-entropy oxide material comprises the following steps:
(1) Rare earth nitrate and metal nitrate are mixed according to the chemical formula RE (Al)1/6Cr1/6Fe1/6Mn1/6M1/6N1/6)O3Accurately weighing the stoichiometric ratio, dissolving in a certain amount of distilled water, and stirring at room temperature to obtain a mixed solution containing rare earth cations and six metal cations, wherein RE is rare earth cation La3+、Pr3+、Nd3+、Sm3+、Gd3+And Y3+M and N are divalent cations Co2+、Ni2+、Mg2+And Zn2+Any two of;
(2) Weighing a certain amount of fuel, adding the mixed solution, and uniformly stirring at room temperature to obtain transparent sol;
(3) Putting the transparent sol into an oven at 80-150 ℃, and evaporating water in the oven to obtain gel;
(4) And (3) placing the gel in high-temperature equipment such as a muffle furnace or a gold furnace and the like, and preserving heat for 0.5-2 hours at 750-1000 ℃ to obtain the novel perovskite type high-entropy oxide material nanocrystalline powder material with high specific surface area and six-membered high-entropy B site.
further, the concentration of the rare earth cation in the step (1) is 1.2-2.4 mol/L.
Further, the concentration of the six metal cations in the step (1) is 0.2 mol/L-0.4 mol/L.
Further, the fuel in step (2) includes one or more of glycine, glucose, hexamethylenetetramine, citric acid, ethylenediamine tetraacetic acid, oxalic acid, and hexamethylene diisocyanate, but is not limited thereto.
Further, the molar ratio of the fuel to the sum of all the cations in the step (2) is 0.5-2: 1.
(III) advantageous effects
The invention provides a novel B-site hexabasic high-entropy perovskite type high-entropy oxide material and a preparation method thereof, wherein the A-site rare earth and the B-site hexabasic high-entropy perovskite type high-entropy oxide material are disclosed and prepared for the first time, and the physical and chemical properties of the material are customized by further regulating and controlling the combination of B-site cations so as to meet some special use requirements; in addition, the perovskite type high-entropy oxide nanocrystalline powder prepared by the solution combustion method has a high specific surface area, a porous structure, uniform chemical composition and a microstructure, is convenient for regulating and controlling the microstructure, and finally realizes the regulation and control of the performance according to the requirement.
Drawings
FIG. 1 shows Sm (Al) in example 11/6Cr1/6Fe1/6Mn1/6Co1/6Ni1/6)O3XRD pictures of the high-entropy oxide powder;
FIG. 2 shows Sm (Al) in example 11/6Cr1/6Fe1/6Mn1/6Co1/6Ni1/6)O3SEM pictures of high entropy oxide powders;
FIG. 3 shows La (Al) in example 21/6Cr1/6Fe1/6Mn1/6Mg1/6Ni1/6)O3SEM pictures of high entropy oxide powders;
FIG. 4 shows Gd (Al) in example 31/6Cr1/6Fe1/6Mn1/6Mg1/6Zn1/6)O3SEM pictures of high entropy oxide powders.
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 with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
example 1:
The novel B-site hexabasic high-entropy perovskite type high-entropy oxide powder is prepared by a solution combustion method, and the chemical composition of the powder is Sm (Al)1/6Cr1/6Fe1/6Mn1/6Co1/6Ni1/6)O3. Weighing corresponding rare earth nitrate and metal nitrate according to the stoichiometric ratio of the molecular formula5.334g of Sm (NO)3)3·9H2O, 0.750g of Al (NO)3)3·9H2O, 0.8004g of Cr (NO)3)3·9H2O, 0.808g Fe (NO)3)3·9H2O, 0.574g of Mn (NO)3)2·4H2O, 0.582g of Co (NO)3)2·6H2O and 0.582g of Ni (NO)3)2·6H2dissolving O in 5mL of distilled water, and uniformly stirring at room temperature to obtain a mixed solution containing a rare earth cation and six metal cations; then 0.901g of glycine is weighed and added into the mixed solution, and the mixture is stirred uniformly; then drying the transparent sol in an oven at 80 ℃, and evaporating water to obtain viscous gel; finally, placing the gel in a muffle furnace, and preserving heat for 2 hours at 1000 ℃ to obtain the gel with a perovskite crystal structure and a specific surface area of 21m2Porous Sm (Al) with an average grain size of 52 nm/g1/6Cr1/6Fe1/6Mn1/6Co1/6Ni1/6)O3And (3) powder materials.
Example 2:
The novel B-site hexabasic high-entropy perovskite type high-entropy oxide powder is prepared by a solution combustion method, and the chemical composition of the powder is La (Al)1/6Cr1/6Fe1/6Mn1/6Mg1/6Ni1/6)O3. Weighing corresponding rare earth nitrate and metal nitrate according to the stoichiometric ratio of molecular formula, specifically 5.196g La (NO)3)3·9H2O, 0.750g of Al (NO)3)3·9H2O, 0.8004g of Cr (NO)3)3·9H2O, 0.808g Fe (NO)3)3·9H2o, 0.574g of Mn (NO)3)2·4H2O、0.513g Mg(NO3)2·6H2O and 0.582g of Ni (NO)3)2·6H2Dissolving O in 10mL of distilled water, and uniformly stirring at room temperature to obtain a mixed solution containing a rare earth cation and six metal cations; then 8.648g of glucose is weighed and added into the mixed solution, and the mixture is stirred evenly; then the transparent sol is mixedDrying in an oven at 100 deg.C, and evaporating to obtain viscous gel; finally, the gel is placed in a muffle furnace and is kept at 850 ℃ for 1h to obtain the gel with the specific surface area of 28m2Perovskite type porous La (Al) with/g and average grain size of 46nm1/6Cr1/6Fe1/6Mn1/6Mg1/6Ni1/6)O3And (3) powder materials.
Example 3:
The novel B-site hexabasic high-entropy perovskite type high-entropy oxide powder is prepared by a solution combustion method, and the chemical composition of the powder is Gd (Al)1/6Cr1/6Fe1/6Mn1/6Mg1/6Zn1/6)O3. Weighing corresponding rare earth nitrate and metal nitrate according to the stoichiometric ratio of molecular formula, specifically 5.416g of Gd (NO)3)3·9H2O, 0.750g of Al (NO)3)3·9H2o, 0.8004g of Cr (NO)3)3·9H2O, 0.808g Fe (NO)3)3·9H2O, 0.574g of Mn (NO)3)2·4H2O、0.513g Mg(NO3)2·6H2o and 0.595g of Zn (NO)3)2·6H2Dissolving O in 8mL of distilled water, and uniformly stirring at room temperature to obtain a mixed solution containing a rare earth cation and six metal cations; then 3.364g of hexamethylenetetramine is weighed and added into the mixed solution, and the mixture is stirred uniformly; then drying the transparent sol in an oven at 150 ℃, and evaporating water to obtain viscous gel; finally, placing the gel in a muffle furnace, and preserving the heat at 750 ℃ for 30min to obtain the gel with the specific surface area of 34m2Perovskite porous Gd (Al) with average grain size of 28nm1/6Cr1/6Fe1/6Mn1/6Mg1/6Zn1/6)O3and (3) powder materials.
In summary, the perovskite-type high-entropy oxide material with rare earth at the A site and six-element high-entropy at the B site, prepared in the embodiments 1 to 3 of the present invention, has a high specific surface area and a porous structure, and a uniform chemical composition and microstructure, and is convenient for the control of the microstructure, and finally, the performance can be controlled as required.
the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A novel B-position hexabasic high-entropy perovskite type high-entropy oxide material is characterized in that the chemical formula is RE (Al)1/ 6Cr1/6Fe1/6Mn1/6M1/6N1/6)O3Wherein RE is rare earth cation La3+、Pr3+、Nd3+、Sm3+、Gd3+And Y3+M and N are divalent cations Co2+、Ni2+、Mg2+And Zn2+Any two of them.
2. The method for preparing a novel B-site hexabasic high-entropy perovskite-type high-entropy oxide material as claimed in claim 1, which is characterized by comprising the following steps:
(1) Rare earth nitrate and metal nitrate are mixed according to the chemical formula RE (Al)1/6Cr1/6Fe1/6Mn1/6M1/6N1/6)O3Accurately weighing the stoichiometric ratio, dissolving in a certain amount of distilled water, and stirring at room temperature to obtain a mixed solution containing rare earth cations and six metal cations, wherein RE is rare earth cation La3+、Pr3+、Nd3+、Sm3+、Gd3+and Y3+M and N are divalent cations Co2+、Ni2+、Mg2+And Zn2+Any two of;
(2) Weighing a certain amount of fuel, adding the mixed solution, and uniformly stirring at room temperature to obtain transparent sol;
(3) Putting the transparent sol into an oven at 80-150 ℃, and evaporating water in the oven to obtain gel;
(4) And (3) placing the gel in high-temperature equipment such as a muffle furnace or a gold furnace and the like, and preserving heat for 0.5-2 hours at 750-1000 ℃ to obtain the novel perovskite type high-entropy oxide material nanocrystalline powder material with high specific surface area and six-membered high-entropy B site.
3. The process for producing a novel perovskite-type high-entropy oxide material having a hexahydric high entropy at the B site according to claim 2, wherein the concentration of the rare earth cation in the step (1) is 1.2 to 2.4 mol/L.
4. the process for producing a novel perovskite-type high-entropy oxide material having a hexahydric high entropy at the B site according to claim 2, wherein the concentration of the six metal cations in the step (1) is 0.2mol/L to 0.4 mol/L.
5. The method for preparing a novel perovskite type high-entropy oxide material with a hexahydric high entropy at the B site according to claim 2, wherein the fuel in the step (2) comprises one or more of glycine, glucose, hexamethylenetetramine, citric acid, ethylenediamine tetraacetic acid, oxalic acid and hexamethylene diisocyanate.
6. The method for preparing a novel perovskite-type high-entropy oxide material with a hexahydric high entropy at the B site according to claim 2, wherein the molar ratio of the fuel to the sum of all the cations in the step (2) is 0.5-2: 1.
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