CN112680740B - Preparation method and application of perovskite oxide catalyst containing alloy particles - Google Patents
Preparation method and application of perovskite oxide catalyst containing alloy particles Download PDFInfo
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention relates to an alloy-containing particleA process for the preparation of a particulate perovskite oxide catalyst comprising the steps of: s1, mixing a raw material and a solvent, and performing ball milling to obtain a mixture A, wherein the raw material comprises Co3O4、La2O3、SrCO3And Fe2O3(ii) a S2, roasting the mixture A to obtain a sample B; s3, roasting the sample B in a mixed gas of reducing gas and inert gas to obtain a product. Through electrochemical tests, when the product obtained by the preparation method of the perovskite oxide catalyst containing the alloy particles is used as an electrocatalyst, overpotential required by hydrogen production through water decomposition can be obviously reduced, so that the electrocatalysis performance is improved, the energy waste is reduced, and the energy utilization rate is improved.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a preparation method and application of a perovskite oxide catalyst containing alloy particles.
Background
With the rapid development of society and science, there is a greater demand and dependence on energy, and conventional energy sources represented by petroleum and coal have been excessively developed and used, and have also brought irreparable problems to the environment. Therefore, the development of new energy is a necessary requirement for social development and realization of a strategy for 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 an ideal sustainable alternative energy source. The hydrogen production by electrolyzing water is popular with enterprises because of the simple, safe and green preparation means of the process. The anodic Oxygen Evolution Reaction (OER) in the hydrogen production by water electrolysis is a multi-step reaction, which causes a great loss of energy because the reaction occurs and a high overpotential is applied to break through the energy barrier activation reaction. Therefore, designing an efficient, cheap, green, safe and high-stability OER catalyst is the core of reducing the overpotential required for hydrogen production by water electrolysis.
The perovskite oxide gradually becomes a research hotspot of the OER electrocatalyst due to the advantages of diversity of constituent elements, stable physicochemical properties, easy structure regulation and the like. The general structural formula of the perovskite oxide is ABO3Wherein, the A site is alkaline earth metal or rare earth and other large atom radius elements, and the B site is transition metal generally. However, the relatively low intrinsic catalytic activity and low electronic conductivity of perovskite oxide materials have been difficult to study. The metal simple substance has excellent OER catalytic performance and electronic conductivity, but is easy to agglomerate in the catalyst preparation process, so that part of active sites are reduced, and the catalytic performance of the metal simple substance cannot be completely released. Resulting in a waste of active sites.
In summary, there is a need to find a new perovskite oxide, a preparation method thereof, and an application thereof in the field of OER. The prepared product is used as an OER catalyst in the field of electrocatalysis and has excellent catalytic performance; meanwhile, the defects that the electronic conductivity of the perovskite oxide is low, the intrinsic catalytic activity is low, and partial active point positions are wasted due to easy agglomeration of metal simple substances and the like can be overcome.
Disclosure of Invention
The invention aims to provide a preparation method of a perovskite oxide catalyst containing alloy particles, wherein the perovskite oxide catalyst containing the alloy particles is prepared from an M alloy and (La)aSrb)xFe1-y-zCoyRuzO3-δComposition wherein M alloy is from (La)aSrb)xFe1-y-zCoyRuzO3-δThe specific component of the metal mixture precipitated in the step (2) is CoFe; delta is an oxygen vacancy (a non-human controlling factor).
The key steps for preparing the product are as follows: under the atmosphere of reducing gas, making M alloy from (La)aSrb)xFe1-y-zCoyRuzO3-δPartially separating outSince the specific mass of the precipitated M alloy is unknown, the values of a, b, x, y and z are all between 0 and 1, so that the composite catalyst material is formed and is suitable for OER. Through electrochemical tests, the product obtained by the preparation method of the perovskite oxide containing the M alloy can be used as an electrocatalyst, and the overpotential required by water decomposition hydrogen production can be obviously reduced, so that the electrocatalysis performance is obviously improved, the energy waste is reduced, and the energy utilization rate is improved.
An object of the present invention is to provide a method for preparing the above perovskite oxide catalyst containing alloy particles, comprising the steps of:
s1, mixing a raw material and a solvent, and performing ball milling to obtain a mixture A, wherein the raw material comprises Co2O3、La2O3、SrCO3And Fe2O3；
S2, roasting the mixture A to obtain a sample B;
s3, roasting the sample B in a mixed gas of reducing gas and inert gas to obtain a product.
Further, the raw material also comprises RuO2。
Further, the perovskite oxide catalyst containing the alloy particles has an average particle diameter of 10 to 300 nm.
Further, the solvent is selected from water, ethanol or acetone.
Further, the volume ratio of the reducing gas to the inert gas is 5:95 to 20: 80.
Further, in step S2, the roasting temperature of the mixture A is 900-1300 ℃, and the roasting time is 3-10 h;
further, in step S3, the sample B is calcined in the mixed gas of the reducing gas and the inert gas at the temperature of 500-900 ℃ for 0.5-5 h.
Further, the reducing gas is hydrogen; the inert gas is selected from one of nitrogen or argon.
Further, the mass ratio of the raw materials to the solvent is 1:4-1: 10.
The invention also aims to provide application of a product prepared by the preparation method of the perovskite oxide catalyst containing the alloy particles in the field of electrocatalysis.
The invention has the following beneficial effects:
(1) compared with the existing perovskite oxide, the product prepared by the preparation method of the perovskite oxide catalyst containing the alloy particles has higher electronic conductivity and obvious electrocatalysis performance, and has lower overpotential compared with a perovskite material not containing M alloy, and the overpotential required by hydrogen production is only 1.57V relative to a reversible hydrogen electrode and is far less than 1.62V not containing M alloy.
(2) The product prepared by the preparation method of the perovskite oxide catalyst containing the alloy particles is not easy to agglomerate in the preparation process of the catalyst, so that the utilization rate of the catalyst is not reduced, and the maximum activity of the catalyst can be released to the maximum extent.
(3) The preparation method of the perovskite oxide catalyst containing the alloy particles disclosed by the invention adopts a solid phase method for synthesis, and compared with a hydrothermal method, a sol-gel method and other synthesis methods, the solid phase method has the advantages of simple synthesis steps, greenness, environmental friendliness, easiness in mass production and industrial production potential.
Drawings
Fig. 1 (a) shows an X-ray diffraction pattern of the perovskite oxide catalyst containing the alloy particles obtained in example 1.
Fig. 1 (b) shows an X-ray diffraction pattern of the perovskite oxide catalyst containing the alloy particles obtained in example 2.
Fig. 1 (c) shows an X-ray diffraction pattern of the perovskite oxide catalyst containing the alloy particles obtained in comparative example 1.
Fig. 1 (d) shows an X-ray diffraction pattern of the perovskite oxide catalyst containing the alloy particles obtained in comparative example 2.
Fig. 2 (a) shows a scanning electron microscope image of the perovskite oxide catalyst containing the alloy particles obtained in example 1.
Fig. 2 (b) shows a scanning electron microscope image of the perovskite oxide catalyst containing the alloy particles obtained in example 2.
Fig. 3 shows a linear scanning energy spectrum picture of the perovskite oxide catalyst containing the alloy particles obtained in example 2.
The graphs (a) to (d) in FIG. 4 show the surface-scan spectral pictures of the perovskite oxide catalyst containing the alloy particles obtained in example 2,
wherein (a) the figure shows a high angle annular dark field image of a perovskite oxide catalyst containing alloy particles; (b) illustrating the area and direction of the line scan energy spectrum scan; (c) illustrating the inclusion of iron elements in the perovskite oxide catalyst comprising the alloy particles; (d) the figure shows that the perovskite oxide catalyst containing the alloy particles contains cobalt element.
Fig. 5 (a) is a graph showing a comparison of the performance of the perovskite oxide catalysts containing alloy particles obtained in example 1 and comparative example 1; fig. 5 (b) is a graph showing a comparison of the performance of the perovskite oxide catalysts containing the alloy particles obtained in example 2 and comparative example 2.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A method of preparing a perovskite oxide catalyst containing alloy particles, comprising the steps of:
s1, adding 0.0005mol of Co2O30.0036mol of La2O30.0018mol of SrCO3And 0.0045mol of Fe2O3Mixing with 10ml of deionized water, and ball-milling for 5 hours in a ball-milling tank at the rotating speed of 300rpm to obtain a mixture A;
s2, roasting the mixture A in a muffle furnace at 900 ℃ for 3h to obtain a sample B;
s3. sample B was fired at 500 ℃ for 0.5h in an atmosphere of a mixed gas of hydrogen and nitrogen (hydrogen: nitrogen ═ 5:95) so that part of the M alloy (CoFe) was separated from (La) byaSrb)xFe1-y-zCoyRuzO3-δThereby obtaining the composite catalyst product.
Fig. 2 (a) shows a scanning electron microscope image of the perovskite oxide catalyst containing the alloy particles obtained in example 1, and illustrates that the perovskite substrate after reduction contains partially precipitated particles.
Example 2
A method of preparing a perovskite oxide catalyst containing alloy particles, comprising the steps of:
s1, adding 0.0005mol of Co2O30.004mol of La2O30.002mol of SrCO30.004mol of Fe2O3And 0.001mol of RuO2Mixing with 15ml of deionized water, and ball-milling for 5 hours in a ball-milling tank at the rotating speed of 300rpm to obtain a mixture A;
s2, roasting the mixture A in a muffle furnace for 10 hours at 1100 ℃ to obtain a sample B;
s3. sample B was fired at 900 ℃ for 5h in an atmosphere of a mixed gas of hydrogen and nitrogen (hydrogen: nitrogen ═ 20:80) so that part of the M alloy (CoFe) was removed from (La) to (La)aSrb)xFe1-y-zCoyRuzO3-δTo obtain the composite catalyst product.
Fig. 2 (b) shows a scanning electron micrograph of the perovskite oxide catalyst containing the alloy particles obtained in example 2, illustrating that the sample of example 2 contains CoFe particles precipitated in situ.
Fig. 3 shows a linear scanning energy spectrum picture of the perovskite oxide catalyst containing the alloy particles obtained in example 2, and it can be seen that the content of Co and Fe element particles in the precipitated M alloy is significantly increased along the arrow scanning direction without other element distribution, indicating that the M alloy is a perovskite oxide material with a CoFe alloy phase.
Fig. 4 are (a) - (d) graphs showing the surface-scan energy spectrum pictures of the perovskite oxide catalyst containing the alloy particles obtained in example 2, wherein the (a) graph shows a high-angle annular dark field image of the perovskite oxide catalyst containing the alloy particles; (b) illustrating the area and direction of the line scan energy spectrum scan; (c) illustrating the inclusion of iron elements in the perovskite oxide catalyst comprising the alloy particles; (d) the figure shows that the perovskite oxide catalyst containing the alloy particles contains cobalt element, indicating that the precipitated perovskite oxide material has a CoFe alloy phase.
Comparative example 1
A method of preparing a perovskite oxide catalyst containing alloy particles, comprising the steps of:
s1, adding 0.0005mol of Co2O30.0036mol of La2O30.0018mol of SrCO3And 0.0045mol of Fe2O3Mixing with 10ml of acetone, and ball-milling for 5 hours in a ball-milling tank at the rotating speed of 300rpm to obtain a mixture A;
s2, roasting the mixture A in a muffle furnace at 900 ℃ for 3h to obtain a sample B;
comparative example 2
A method of preparing a perovskite oxide catalyst containing alloy particles, comprising the steps of:
s1, adding 0.0005mol of Co2O30.004mol of La2O30.002mol of SrCO30.004mol of Fe2O3And 0.001mol of RuO2Mixing with 15ml of absolute ethyl alcohol, and ball-milling for 5 hours in a ball-milling tank at the rotating speed of 300rpm to obtain a mixture A;
s2, roasting the mixture A in a muffle furnace for 10 hours at 1100 ℃ to obtain a sample B;
fig. 1 (a) to (d) show X-ray diffraction patterns of the perovskite oxide catalysts containing alloy particles obtained in example 1, example 2, comparative example 1 and comparative example 2, respectively, from which it can be found that example 1 and example 2 after treatment with a reducing gas show a peak at an angle of 46 to 47 °, indicating that example 1 and example 2 are perovskite oxide materials containing a CoFe alloy phase, whereas comparative example 1 and comparative example 2 show no characteristic peak in this range, indicating that comparative example 1 and comparative example 2 do not show CoFe.
In order to test the technical effect of the product prepared by the preparation method of the perovskite oxide catalyst containing the alloy particles in the field of electrocatalysis, the following test examples are provided.
The testing procedure was as follows:
(1) pretreatment of the electrocatalyst: the products obtained in examples 1 to 5 above, and as comparative material RuO2Respectively weighing 5.0mg of the six samples, uniformly mixing the six samples with 5.0mg of XC-72, adding 0.5mL of Nafion solution and 1.5mL of isopropanol into the samples respectively to obtain mixed solutions, and ultrasonically oscillating each mixed solution in an ultrasonic instrument for 60min to obtain a sample to be detected.
(2) Dripping 50 μ L of the above six samples to a clean area of 0.196cm2Drying the surface of the glassy carbon electrode in the air for 1h to obtain a required working electrode, testing the OER performance of the electrocatalytic performance by adopting a three-electrode system, wherein the working electrode is a glassy carbon electrode, the counter electrode is a Pt sheet electrode, the reference electrode is an Ag/AgCl electrode, the electrolyte is a 1mol/L potassium hydroxide solution, and introducing oxygen into the electrolyte for 30 minutes before testing, wherein the scanning voltage range of Cyclic Voltammetry (CV) is 0.0-1.0V, the scanning rate is 50mV/s, the scanning voltage range of linear voltammetry (LSV) is 0.0-1.0V, the scanning rate is 5mV/s, and the contrast current density is 10mA/cm2Corresponding to the overpotential.
The results obtained are shown in table 1.
TABLE 1 results of overpotential test for samples obtained in examples 1-2 and comparative examples 1-2 as a point catalyst
Fig. 5 (a) is a graph showing a comparison of the performance of the perovskite oxide catalysts containing alloy particles obtained in example 1 and comparative example 1; fig. 5 (b) is a graph showing a comparison of the performance of the perovskite oxide catalysts containing the alloy particles obtained in example 2 and comparative example 2. As can be seen from Table 1, the current density was 10mA/cm2The potentials of example 1 and example 2 are respectively lower than those of comparative example 1 and comparative example 2, which shows that the perovskite oxide catalyst containing the alloy particles has more excellent catalytic performance and remarkable advantages. The product prepared by the preparation method of the perovskite oxide catalyst containing the alloy particles, disclosed by the invention, is applied to OER as an electrocatalyst, and has a wide commercial prospect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (7)
1. A preparation method of an alloy particle-containing perovskite oxide electrocatalytic oxygen evolution catalyst is characterized by comprising the following steps:
s1, mixing a raw material and a solvent, and performing ball milling to obtain a mixture A, wherein the raw material comprises Co2O3、La2O3、SrCO3And Fe2O3；
S2, roasting the mixture A to obtain a sample B;
s3, roasting the sample B in a mixed gas of reducing gas and inert gas to obtain a product;
the mass ratio of the raw materials to the solvent is 1:4-1: 10;
in step S3, the roasting temperature of the sample B in the mixed gas of reducing gas and inert gas is 500-900 ℃, and the roasting time is 0.5-5 h;
the solvent is selected from water, ethanol or acetone;
the perovskite oxide electrocatalytic oxygen evolution catalyst containing the alloy particles is prepared from a CoFe alloy and (La)aSrb)xFe1-yCoyO3-δForming; wherein δ is an oxygen vacancy; a. the values of b, x and y are all more than 0 and less than 1;
the volume ratio of the reducing gas to the inert gas is 5:95-20: 80.
2. The method of claim 1, wherein the feedstock further comprises RuO2。
3. The method for producing the alloy particle-containing perovskite oxide electrocatalytic oxygen evolution catalyst as set forth in claim 1, wherein the average particle diameter of the alloy particle-containing perovskite oxide electrocatalytic oxygen evolution catalyst is 10 to 300 nm.
4. The preparation method of the alloy particle-containing perovskite oxide electrocatalytic oxygen evolution catalyst as claimed in claim 1, wherein in step S2, the calcination temperature of the mixture A is 900-1300 ℃, and the calcination time is 3-10 h.
5. The method for producing a perovskite oxide electrocatalytic oxygen evolution catalyst containing alloy particles as set forth in claim 1, wherein the reducing gas is hydrogen; the inert gas is selected from nitrogen or argon.
6. The perovskite oxide electrocatalytic oxygen evolution catalyst containing the alloy particles prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the alloy particle-containing perovskite oxide electrocatalytic oxygen evolution catalyst according to claim 6 in the field of electrocatalytic oxygen evolution.
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| CN109759077B (en) * | 2019-01-08 | 2021-12-07 | 南京航空航天大学 | Perovskite oxide catalyst and preparation method and application thereof |
| CN109921043B (en) * | 2019-02-26 | 2021-10-08 | 五邑大学 | Electro-catalyst of B-doped perovskite oxide and preparation method thereof |
| CN111477881B (en) * | 2020-03-19 | 2022-05-24 | 华南理工大学 | NiFe alloy nanoparticle coated Pr0.8Sr1.2(FeNi)O4-δMaterial and method for producing the same |
| CN111644183B (en) * | 2020-05-12 | 2023-07-28 | 五邑大学 | IrO-containing material 2 Preparation method and application of perovskite oxide |
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