CN115572987A - Surface-modified perovskite oxide electrocatalyst and preparation method and application thereof - Google Patents
Surface-modified perovskite oxide electrocatalyst and preparation method and application thereof Download PDFInfo
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The invention discloses a surface modified perovskite oxide electrocatalyst and a preparation method and application thereof. The surface-modified perovskite oxide is La 1‑x Sr x NiO 3‑δ Wherein 0 is<x is less than or equal to 0.40; the surface modified perovskite oxide has flaky NiO on the surface. Through electrochemical tests, the surface modified perovskite oxide La prepared by the method 1‑x Sr x NiO 3‑δ The electro-catalyst can obviously reduce the overpotential required for generating OER, thereby obviously improving the electro-catalytic performance. Compared with the traditional electrocatalyst prepared by precious metals, the perovskite oxide electrocatalyst prepared by the method has the advantages of greatly reduced cost, simple preparation process, low requirement on the preparation process, stable product structure, green and pollution-free process, and suitability for being subjected to sol-gel method preparation of perovskite oxide and surface modification by corrosion of acid solutionMass production.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a surface-modified perovskite oxide electrocatalyst, and a preparation method and application thereof.
Background
Along with the increasing dependence on energy, the problems of energy exhaustion and environmental pollution are also increasingly highlighted. Current energy supplies are primarily petroleum, coal, natural gas, and renewable resources. The first three energy supplies account for 80% of the total energy demand, indicating that conventional fossil fuels are currently the primary energy source. Therefore, the search for renewable energy sources is of great significance for realizing sustainable development. As a novel energy source, the hydrogen has the advantages of large combustion value, clean and pollution-free combustion products, convenient storage and the like, and is the most ideal sustainable alternative energy source. Among many hydrogen production means, hydrogen production by electrolyzing water is the cleanest, safe and efficient means. Electrochemical water splitting includes Oxygen Evolution Reaction (OER) at the anode and hydrogen evolution reaction at the cathode. Where the oxygen evolution reaction at the anode requires four electron transfer, its complex intermediates and slow kinetic rates severely limit the application of electrochemical water splitting. The reaction often needs to be carried out by applying higher Overpotential (eta), and the Gibbs free energy required by the reaction can be reduced by using the catalyst, so that the Overpotential eta is reduced. Therefore, the key point for improving the hydrogen production efficiency by electrolyzing water is to research out an efficient OER catalyst.
The current primary OER catalyst material is IrO 2 Or RuO 2 The Ir or Ru has ultrahigh catalytic activity, but the commercial application of the Ir or Ru is limited due to the reasons of small earth abundance, poor stability and the like. Thus, researchers have increasingly looked at other high performance non-noble metal electrocatalysts and non-metal catalysts. The perovskite oxide in the perovskite oxide is a research focus due to low cost, flexible composition and high intrinsic activity. And the perovskite oxide can also adjust the catalytic performance through internal and external combination: the internal regulation is mainly completed by means of regulating an electronic structure, oxygen vacancy, doping and the like; the external regulation is mainly realized through composite materials, material nanocrystallization, morphology optimization, porous structure manufacturing and the like. However, the intrinsic activity of perovskite oxide is low, the electronic conductivity is not high, and the long-term stability is poor, which has become a bottleneck limiting the wide use of perovskite oxide. The design of a perovskite oxide catalyst with high intrinsic activity, high electronic conductivity and excellent stability is the key to solve the problem.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a surface modified perovskite oxide electrocatalyst and a preparation method and application thereof. The invention provides perovskite oxide (La) 1-x Sr x NiO 3-δ ) The surface of the perovskite oxide electrocatalyst is provided with flaky NiO, and the overpotential required for OER generation can be obviously reduced through an electrochemical test, so that the electrocatalytic performance is obviously improved. The preparation method has the advantages of simple process, low cost and environmental protection.
According to one aspect of the present invention, a surface-modified perovskite oxide is provided, which is prepared by the above preparation method.
The chemical formula of the surface modified perovskite oxide prepared by the method is La 1-x Sr x NiO 3-δ Wherein 0 is<x ≦ 0.40, e.g., x =0.05, 0.1, 0.15, 0.2, 0.3, or 0.4, or any value in the interval thereof; preferably, 0<x≤0.20。
According to another aspect of the present invention, a method of preparing a surface-modified perovskite oxide is provided.
The method comprises the following steps:
(1) Dissolving the raw materials; heating and stirring to make the solution gel to obtain a sample A; the raw materials comprise soluble salts of La ions, ni ions and Sr ions.
(2) Drying and grinding the sample A to obtain a powder sample B;
(3) Calcining and grinding the sample B to obtain a powder sample C;
(4) And putting the sample C in an acid solution, corroding, washing and drying to obtain a final product.
In the step (1), soluble salts of La ions, ni ions and Sr ions as raw materials are added according to La 1-x Sr x NiO 3-δ The stoichiometric ratio of each element is measured, wherein 0<x≤0.40。
Perovskite oxygen prepared by the inventionCompound La 1-x Sr x NiO 3-δ Doping a certain amount of Sr element at the A site promotes the dissolution of the A site element of the perovskite oxide in an acid solution. Experiments show that Sr is more easily subjected to selective corrosion compared with La, so that more B-site Ni elements are precipitated and oxidized, and active materials such as NiO and the like are generated on the surface. NiO and LaNiO generated on the surface after selective corrosion 3 The perovskite has a synergistic effect in catalysis, so that the proportion of La and Sr needs to be reasonably regulated and controlled, and the amount of NiO covered on the surface is controlled, so that the calcium-titanium mineral catalyst with better OER performance is obtained.
Perovskite oxide La 1-x Sr x NiO 3-δ The perovskite oxide La modified by the surface modification is electrochemically tested 1- x Sr x NiO 3-δ The catalyst is used as an electrocatalyst, and can obviously reduce the overpotential required for OER generation, thereby obviously improving the electrocatalytic performance.
Preferably, the soluble salt is one or more of nitrate, acetate and sulphate.
Preferably, the raw materials, water and citric acid are mixed and dissolved to form a uniform solution; further preferably, the starting material is added to water first, followed by the addition of citric acid.
Preferably, wherein the ratio of the total moles of metal ions to the moles of citric acid is 1:1.5-3; preferably, about 1:2.
preferably, the water used is ultrapure water.
The invention does not use cross-linking agent in the process of forming gel, is more beneficial to forming phase, and the calcined material can not cause impure phase generation.
Preferably, the heating and stirring in step (1) is constant temperature heating and stirring. Preferably, the heating temperature is 80-100 ℃; preferably, the rotation speed of stirring is 500-800r/min.
In the step (2), the drying temperature is 180-250 ℃; the time is 3-6 hours. Specifically, the drying temperature can be 180 ℃, 200 ℃, 220 ℃, 230 ℃ or 250 ℃; the time may be 3, 4, 5 or 6 hours.
In step (3), sample B was calcined in an air atmosphere. In some embodiments, the temperature of calcination is from 600 to 900 ℃; the time is 5-8 hours. Specifically, the temperature of calcination may be 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ or 900 ℃, preferably 650 to 750 ℃, more preferably 700 ℃; the time of calcination may be 5, 6, 7 or 8 hours.
Preferably, the grinding in step (3) is manual grinding or mechanical grinding.
In step (4), the ratio of the mass of the sample C to the volume of the acidic solution was 1g:20-30mL, e.g., 1g:25mL. The proper acid concentration ensures that a small amount of metal element is dissolved without destroying the overall structure of the material.
Preferably, the acidic solution includes, but is not limited to, a dilute nitric acid solution or a tartaric acid solution.
Preferably, the concentration of the acidic solution is 0.2-0.4mol/L, such as 0.3mol/L.
Preferably, in the step (4), the sample C is placed in an acid solution to be subjected to normal-temperature corrosion; further preferably, the time of etching is 1-10 hours, for example, 1, 3, 4, 5, 6, 8 or 10 hours.
Preferably, after the etching is performed, the final product is obtained by washing with water 3-6 times and then drying at 60-100 ℃ for 6-12 hours.
The perovskite oxide La prepared by the invention 1-x Sr x NiO 3-δ The surface modified perovskite oxide electrocatalyst is obtained by simply adjusting parameters such as the content of Sr element doped at A site, the concentration of acid solution, corrosion time and the like, and the parameters have important influence on the performance of the catalyst.
According to a further aspect of the present invention there is provided a surface-modified perovskite oxide electrocatalyst comprising the surface-modified perovskite oxide as described above.
The surface-modified perovskite oxide electrocatalyst of the invention can be prepared by the following method:
and (3) mixing the product obtained in the step (4) with carbon powder (XC-72R), adding Nafion solution and isopropanol, and carrying out ultrasonic oscillation for 30-60 minutes to mix so as to obtain the surface-modified perovskite oxide electrocatalyst.
The purpose of this preparation method was to prepare surface-modified perovskite oxide electrocatalysts into catalyst inks for electrocatalysis tests.
Preferably, the mass ratio of the product obtained in the step (4) to the carbon powder (XC-72R) is 1:0.2 to 1, preferably 1:1; the mass of the product to volume ratio of Nafion was 1g:0.05-0.2L, preferably 1g:0.1L; the mass of the product and the volume ratio of isopropanol were 1g:0.1-0.8L, preferably 1g:0.3L. Wherein the mass concentration of the Nafion solution can be 0.1-1%, preferably 0.5%.
According to yet another aspect of the present invention, there is provided a use of a surface-modified perovskite oxide electrocatalyst in the field of electrocatalysis.
The invention has the following beneficial effects:
1. the invention synthesizes perovskite oxide La 1-x Sr x NiO 3-δ The perovskite oxide with modified surface is obtained by the erosion treatment of the acid solution, the flaky NiO is formed on the surface of the perovskite oxide, and the flaky NiO is used as an electrocatalyst, so that the overpotential required by OER can be obviously reduced, and the electrocatalytic performance is obviously improved.
2. Compared with the traditional electrocatalyst prepared by noble metals, the perovskite oxide electrocatalyst prepared by preparing the perovskite oxide by a sol-gel method and carrying out surface modification by corrosion of an acidic solution has the advantages of greatly reduced cost, simple preparation process, low requirement on the preparation process, stable product structure, green and pollution-free process and suitability for mass production.
Drawings
FIG. 1 is the perovskite oxide La of example 1 0.95 Sr 0.05 NiO 3-δ XRD patterns of the samples before acid etching and after 5 hours of etching; wherein PDF #34-1181 is perovskite oxide LaNiO 3 A standard card;
FIG. 2 is the perovskite oxide La of example 1 0.95 Sr 0.05 NiO 3-δ Sample before acid etching (a)And SEM image of (b) after 5 hours of etching;
FIG. 3 is perovskite oxide La 0.95 Sr 0.05 NiO 3-δ Linear Sweep Voltammetry (LSV) plots of OER performance of the samples after acid etching for various times (0, 1, 3, 5, 10 hours).
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares a surface-modified perovskite oxide electrocatalyst, and the specific process comprises the following steps:
(1) 0.019mol of La (NO) 3 ) 3 ·6H 2 O、0.02mol Ni(NO 3 ) 2 ·6H 2 O and 0.001mol Sr (NO) 3 ) 2 Pouring into a beaker filled with 150mL of ultrapure water, and then adding the solution according to La 0.95 Sr 0.05 NiO 3-δ The molar ratio of the metal ions to the citric acid in (1): 2, adding 0.08mol of citric acid to fully dissolve the citric acid, and finally putting the beaker into an oil bath pot to heat (the temperature is 80 ℃) and stir to enable the solution to be in a gel state to obtain a sample A;
(2) Placing the sample A in a forced air drying oven for drying at 250 ℃ for 3 hours, and grinding to obtain a powder sample B;
(3) Calcining the sample B in a muffle furnace at 700 ℃ for 5 hours, and then manually grinding for 20-30 minutes to obtain phase-formed La 0.95 Sr 0.05 NiO 3-δ Powder sample C;
(4) Sample C was placed in 0.3mol/L dilute HNO 3 In the solution, the ratio of the mass of sample C to the volume of the acidic solution was 0.3g:6mL, normal temperature corrosion time of 1, 3, 5 and 10 hours, washing with ultrapure water for 5 times, and drying at 80 DEG CDrying in a drying oven for 10 hours to obtain the final product, namely the surface modified perovskite oxide;
(5) Mixing 5mg of prepared surface-modified perovskite oxide with 5mg of XC-72R, adding 0.5mL of Nafion solution (0.5 wt.%) and 1.5mL of isopropanol, and carrying out ultrasonic oscillation for 30-60 minutes to mix, thereby obtaining the surface-modified perovskite oxide electrocatalyst.
Example 2
The embodiment prepares a surface-modified perovskite oxide electrocatalyst, and the specific process comprises the following steps:
(1) 0.018mol of La (NO) 3 ) 3 ·6H 2 O、0.02mol Ni(NO 3 ) 2 ·6H 2 O and 0.002mol of Sr (NO) 3 ) 2 Pouring into a beaker filled with 150mL of ultrapure water, and then adding the solution according to La 0.9 Sr 0.1 NiO 3-δ The molar ratio of the metal ions to the citric acid in (1): 2, adding 0.08mol of citric acid to fully dissolve the citric acid, and finally putting the beaker into an oil bath pot to heat (the temperature is 80 ℃) and stir to enable the solution to be in a gel state to obtain a sample A;
(2) Placing the sample A in a forced air drying oven for drying at 250 ℃ for 3 hours, and grinding to obtain a powder sample B;
(3) Calcining the sample B in a muffle furnace at 700 ℃ for 5 hours, and then manually grinding for 20-30 minutes to obtain phase-formed La 0.9 Sr 0.1 NiO 3-δ Powder sample C;
(4) Sample C was placed in 0.3mol/L dilute HNO 3 In the solution, the ratio of the mass of sample C to the volume of the acidic solution was 0.3g:6mL, the normal temperature corrosion time is 1, 3, 5 and 10 hours, the obtained product is washed for 5 times by using ultrapure water, and the obtained product is dried in a drying oven at the temperature of 80 ℃ for 10 hours to obtain a final product, namely the surface-modified perovskite oxide;
(5) Mixing 5mg of prepared surface-modified perovskite oxide with 5mg of XC-72R, adding 0.5mL of Nafion solution (0.5 wt.%) and 1.5mL of isopropanol, and carrying out ultrasonic oscillation for 30-60 minutes to mix, thereby obtaining the surface-modified perovskite oxide electrocatalyst.
Example 3
The embodiment prepares a surface-modified perovskite oxide electrocatalyst, and the specific process comprises the following steps:
1) 0.017mol of La (NO) 3 ) 3 ·6H 2 O、0.02mol Ni(NO 3 ) 2 ·6H 2 O and 0.003mol Sr (NO) 3 ) 2 Pouring into a beaker filled with 150mL of ultrapure water, and then adding the solution according to La 0.85 Sr 0.15 NiO 3-δ The molar ratio of the metal ions to the citric acid in (1): 2, adding 0.08mol of citric acid to fully dissolve the citric acid, and finally putting the beaker into an oil bath pot to heat (the temperature is 80 ℃) and stir to enable the solution to be in a gel state to obtain a sample A;
(2) Placing the sample A in a forced air drying oven for drying at 250 ℃ for 3 hours, and grinding to obtain a powder sample B;
(3) Calcining the sample B in a muffle furnace at 700 ℃ for 5 hours, and then manually grinding for 20-30 minutes to obtain phase-formed La 0.85 Sr 0.15 NiO 3-δ Powder sample C;
(4) Sample C was placed in 0.3mol/L dilute HNO 3 In solution, the ratio of the mass of sample C to the volume of the acidic solution was 0.3g:6mL, the normal temperature corrosion time is 1, 3, 5 and 10 hours, the obtained product is washed by ultrapure water for 5 times and dried in a drying oven at the temperature of 80 ℃ for 10 hours to obtain the final product, namely the surface modified perovskite oxide;
(5) Mixing 5mg of prepared surface-modified perovskite oxide with 5mg of XC-72R, adding 0.5mL of Nafion solution (0.5 wt.%) and 1.5mL of isopropanol, and carrying out ultrasonic oscillation for 30-60 minutes to mix, thereby obtaining the surface-modified perovskite oxide electrocatalyst.
Example 4
The embodiment prepares a surface-modified perovskite oxide electrocatalyst, and the specific process comprises the following steps:
(1) 0.016mol of La (NO) 3 ) 3 ·6H 2 O、0.02mol Ni(NO 3 ) 2 ·6H 2 O and 0.004mol of Sr (NO) 3 ) 2 Pouring into a beaker filled with 150mL of ultrapure water, and then adding the solution according to La 0.8 Sr 0.2 NiO 3-δ Of (2)Molar ratio of ion to citric acid 1:2, adding 0.08mol of citric acid to fully dissolve the citric acid, and finally putting the beaker into an oil bath pot to heat (the temperature is 80 ℃) and stir to enable the solution to be in a gel state to obtain a sample A;
(2) Placing the sample A in a forced air drying oven for drying at 250 ℃ for 3 hours, and grinding to obtain a powder sample B;
(3) Calcining the sample B in a muffle furnace at 700 ℃ for 5 hours, and then manually grinding for 20-30 minutes to obtain phase-formed La 0.8 Sr 0.2 NiO 3-δ Powder sample C;
(4) Sample C was placed in 0.3mol/L dilute HNO 3 In solution, the ratio of the mass of sample C to the volume of the acidic solution was 0.3g:6mL, the normal temperature corrosion time is 1, 3, 5 and 10 hours, the obtained product is washed by ultrapure water for 5 times and dried in a drying oven at the temperature of 80 ℃ for 10 hours to obtain the final product, namely the surface modified perovskite oxide;
(5) Mixing 5mg of prepared surface-modified perovskite oxide with 5mg of XC-72R, adding 0.5mL of Nafion solution (0.5 wt.%) and 1.5mL of isopropanol, and carrying out ultrasonic oscillation for 30-60 minutes to mix, thereby obtaining the surface-modified perovskite oxide electrocatalyst.
Example 5
The embodiment prepares a surface-modified perovskite oxide electrocatalyst, and the specific process comprises the following steps:
(1) 0.019mol of La (NO) 3 ) 3 ·6H 2 O、0.02mol Ni(NO 3 ) 2 ·6H 2 O and 0.001mol Sr (NO) 3 ) 2 Pouring into a beaker filled with 150mL of ultrapure water, and then adding the solution according to La 0.95 Sr 0.05 NiO 3-δ The molar ratio of the metal ions to the citric acid in (1): 2, adding 0.08mol of citric acid to fully dissolve the citric acid, and finally putting the beaker into an oil bath pot to heat (the temperature is 80 ℃) and stir to enable the solution to be in a gel state to obtain a sample A;
(2) Placing the sample A in a forced air drying oven for drying at 250 ℃ for 3 hours, and grinding to obtain a powder sample B;
(3) Sample B was placed in a muffle furnaceCalcining at 700 deg.C for 5 hr, and manually grinding for 20-30 min to obtain phase-formed La 0.95 Sr 0.05 NiO 3-δ Powder sample C;
(4) Sample C was placed in 0.2mol/L dilute HNO 3 In the solution, the ratio of the mass of sample C to the volume of the acidic solution was 0.3g:6mL, the normal temperature corrosion time is 1, 3, 5 and 10 hours, the obtained product is washed by ultrapure water for 5 times and dried in a drying oven at the temperature of 80 ℃ for 10 hours to obtain the final product, namely the surface modified perovskite oxide;
(5) Mixing 5mg of prepared surface-modified perovskite oxide with 5mg of XC-72R, adding 0.5mL of Nafion solution (0.5 wt.%) and 1.5mL of isopropanol, and carrying out ultrasonic oscillation for 30-60 minutes to mix, thereby obtaining the surface-modified perovskite oxide electrocatalyst.
Test examples
This experimental example tested the performance of the surface-modified perovskite oxide electrocatalyst prepared in the example. Wherein:
20 mul of the surface modified perovskite oxide electrocatalyst is absorbed by a pipette and dripped to a clean area of 0.196cm 2 And drying the surface of the glassy carbon electrode in the air for 10 hours to obtain the required working electrode, and testing the electrocatalysis performance by adopting a three-electrode system.
The electrochemical performance of the products prepared in the above examples was tested using a three-electrode system. Wherein the working electrode is a glassy carbon electrode, the reference electrode is a saturated Hg/HgO electrode, and the counter electrode is a graphite electrode. Electrochemical testing was performed using an electrochemical workstation (Bio-Logic SAS) by first passing oxygen for 30 minutes before testing in an oxygen-saturated 1mol/LKOH solution. When OER electrochemical performance test is carried out, firstly, a cyclic voltammetry Curve (CV) is scanned, the scanning interval is 0.1V to 0.6V vs. Hg/HgO, and the scanning speed is 100mV/s; and performing linear sweep voltammetry test, wherein the sweep interval is 0.1V to 1.1V vs. Hg/HgO, the sweep rate is 5mV/s, and the rotating speed of the rotating disc device is controlled to be 1600rpm.
And (3) testing results:
examples 1-5 were tested to successfully prepare the surface-modified perovskite oxide electrocatalysts of the present invention in which the flaky NiO was formed on the surface of the surface-modified perovskite oxide electrocatalysts. Wherein:
FIG. 1 shows the perovskite oxide La of example 1 0.95 Sr 0.05 NiO 3-δ The sample is diluted HNO at 0.3mol/L 3 XRD patterns of the solution before (a) and after 5 hours (b), wherein PDF #34-1181 is perovskite oxide LaNiO 3 A standard card. Diffraction peaks at 37, 43, 63 and 75 degrees were observed for the sample after acid etching compared to before acid etching, corresponding to the diffraction peaks for NiO, indicating that the surface of the sample was changed after acid etching.
FIG. 2 shows the perovskite oxide La of example 1 0.95 Sr 0.05 NiO 3-δ The sample is diluted HNO at 0.3mol/L 3 SEM images of the solution before etching (a) and after etching for 5 hours (b). It is obvious from the figure that the surface appearance of the material after acid corrosion is changed, and a plurality of flaky substances appear.
FIG. 3 shows the perovskite oxide La of example 1 0.95 Sr 0.05 NiO 3-δ The sample is diluted HNO at 0.3mol/L 3 Linear Sweep Voltammetry (LSV) plots of the OER performance after electrochemical testing after the solution corrosion for different times (0, 1, 3, 5, 10 hours). As can be seen from the figure, the samples etched by acid for 1, 3, 5, 10 hours at a current density of 10mA cm –2 The corrosion inhibitor has overpotentials of 670mV, 500mV, 450mV and 380mV respectively, along with acid corrosion, the performance of the electrocatalytic OER is far better than that before non-corrosion, and along with the increase of corrosion time, the performance of the electrocatalytic OER is gradually better; this indicates that the perovskite oxide La was treated by acid 1-x Sr x NiO 3-δ Surface modified perovskite oxide (La) with flaky NiO substance generation 1-x Sr x NiO 3-δ ) The OER performance of the electrocatalyst is obviously improved. Furthermore, it has been found experimentally that as the corrosion time continues to be extended, above 10 to hours (e.g. 12 hours), the OER performance of the resulting perovskite oxide electrocatalyst tends to be stable.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A surface-modified perovskite oxide, characterized in that the surface-modified perovskite oxide has the chemical formula La 1-x Sr x NiO 3-δ Wherein 0 is<x is less than or equal to 0.40; the surface modified perovskite oxide has flaky NiO on the surface.
2. The method of preparing a surface-modified perovskite oxide as claimed in claim 1, comprising the steps of:
(1) Dissolving the raw materials; heating and stirring to make the solution gel to obtain a sample A; the raw materials comprise soluble salts of La ions, ni ions and Sr ions;
(2) Drying and grinding the sample A to obtain a powder sample B;
(3) Calcining and grinding the sample B to obtain a powder sample C;
(4) And putting the sample C in an acid solution, corroding, washing and drying to obtain a final product.
3. The method of claim 2, wherein the soluble salt is one or more of nitrate, acetate and sulfate.
4. The production method according to claim 2, wherein in the step (1), the raw material, water and citric acid are mixed and dissolved; wherein the molar ratio of the total mole number of the metal ions to the mole number of the citric acid is 1:1.5-3.
5. The production method according to claim 2, wherein the heating and stirring in the step (1) is constant-temperature heating and stirring; the heating temperature is 80-100 ℃; the stirring speed is 500-800r/min.
6. The method according to claim 2, wherein in the step (2), the temperature of drying is 180 to 250 ℃; the time is 3 to 6 hours; in step (3), sample B is calcined in an air atmosphere; the calcining temperature is 600-900 ℃; the time is 5-8 hours.
7. The method according to claim 2, wherein in the step (4), the ratio of the mass of the sample C to the volume of the acidic solution is 1g:20-30mL; the concentration of the acid solution is 0.2-0.4mol/L; the acid solution is dilute nitric acid solution or tartaric acid solution.
8. The production method according to claim 2, wherein in the step (4), the etching time is 1 to 10 hours; then washing with water for 3-6 times, and drying at 60-100 deg.C for 6-12 hr to obtain the final product.
9. A surface-modified perovskite oxide electrocatalyst, characterized in that it comprises the surface-modified perovskite oxide according to claim 1.
10. Use of the surface-modified perovskite oxide electrocatalyst according to claim 9 in the field of electrocatalysis.
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