CN114875432A - Perovskite type oxygen reduction electrocatalyst and preparation and application thereof - Google Patents
Perovskite type oxygen reduction electrocatalyst and preparation and application thereof Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 30
- 239000001301 oxygen Substances 0.000 title claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010411 electrocatalyst Substances 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 57
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 24
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
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- 238000003786 synthesis reaction Methods 0.000 claims description 8
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- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000005204 segregation Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
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- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical group C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a perovskite type catalyst for two-electron oxygen reduction electrocatalysis, which has a Ruddlesden-Popper phase structure and a chemical formula of Ln 2 NiO 4+δ Wherein Ln is one or more of La, Pr or Nd. The invention also provides a preparation method of the catalyst, which comprises the following steps: 1) dissolving water-soluble rare earth metal salt and Ni (NO) 3 ) 2 6H2O dissolved in water to form an aqueous solution; adding citric acid and ethylene glycol into the aqueous solution to form a mixed solution, heating the mixed solution at 60-90 ℃ to obtain gel, and removing organic components; 2) and calcining the precursor at high temperature in an inert gas atmosphere, and ball-milling and drying a calcined product to obtain the catalyst. The perovskite catalyst provided by the invention is used for preparing hydrogen peroxide by electrocatalytic reduction of oxygen, and the generation selectivity of the hydrogen peroxide is more than 50%.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to an oxygen reduction electrocatalyst and a preparation technology thereof.
Background
Hydrogen peroxide (H) 2 O 2 ) Is an important green chemical product, and has wide application, including medical, military and industrial application, such as disinfection, waste water treatment, chemical synthesis, etc. At present the industryThe main method for preparing hydrogen peroxide is 2-ethyl anthraquinone, which has high energy consumption, complex process and high cost. In contrast, H is produced by a two-electron electrochemical oxygen reduction process using a simple electrochemical device 2 O 2 Effectively avoid H 2 O 2 Large scale transportation of (2) to (H) 2 O 2 The product is a novel H with low energy consumption, low manufacturing cost and high safety 2 O 2 And (3) a synthesis technology. However, at present, there is still a lack of electrocatalysts having high catalytic performance and low cost.
Although noble metals and their alloys, for H 2 O 2 The electrochemical preparation has high selectivity. However, the high cost and rarity of precious metal components make future large-scale deployments challenging. And therefore an increasing number of researchers have turned their attention to non-noble metal catalysts. Perovskite-like catalysts are used as catalysts for a variety of electrochemical reactions due to their physical and chemical properties. It has the advantages of low cost, high stability of crystal structure, ingenious flexibility of catalyst design and the like. However, the perovskite-type catalyst is used for electrocatalytic reduction of oxygen (O) 2 ) Preparation of hydrogen peroxide (H) 2 O 2 ) Has not been reported.
Disclosure of Invention
Based on the prior art, the invention aims to provide a perovskite catalyst and a preparation method thereof, the catalyst is used for generating hydrogen peroxide through a 2 e-oxygen reduction reaction, and has the characteristics of high efficiency and high selectivity.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
The invention firstly provides a perovskite type catalyst for two-electron oxygen reduction electrocatalysis, the perovskite type catalyst has a Ruddlesden-Popper phase structure, and the chemical formula is as follows: ln 2 NiO 4+δ Wherein Ln is selected from one or more of rare earth metal elements La, Pr or Nd; wherein the stoichiometric ratio of the sum of the stoichiometric ratios of the rare earth elements to Ni is 2:1, e.g. PrLaNiO 4+δ 。
Furthermore, the perovskite type catalyst is micron particles, the particles are uniform, the average particle size of a single particle is 1-5 mu m, the surface of the particle is flat, and a plurality of particles are aggregated into large particles of about 10 mu m.
Further, in the perovskite catalyst, each element was uniformly distributed, and no element segregation phenomenon was observed.
The invention also provides a preparation method of the perovskite catalyst, which comprises the following preparation steps:
s1: preparing a desired material comprising: one or more of water-soluble rare earth metal salts, citric acid, ethylene glycol and Ni (NO) 3 ) 2 ·6H 2 And O. Wherein the water-soluble rare earth metal salt is selected from one or more of nitrate, acetate, sulfate and the like of rare earth metal elements La, Pr or Nd, such as: preparation of perovskite catalyst Pr 2 NiO 4+δ Preparation of nitrate Pr (NO) 3 ) 3 ·6H 2 O; preparation of PrLaNiO 4+δ Preparation of nitrate Pr (NO) 3 ) 3 ·6H 2 O and La (NO) 3 ) 3 ·6H 2 O）、Ni(NO 3 ) 2 ·6H 2 O）。
S2, preparation of a precursor: mixing the rare earth metal salt with Ni (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water to form an aqueous solution; wherein the rare earth metal salt and Ni (NO) 3 ) 2 ·6H 2 O is added according to the stoichiometric ratio of each rare earth metal element and Ni in the chemical formula of the target product, namely the perovskite catalyst; for example, Pr is the target product 2 NiO 4+δ Addition of Pr (NO) can be used 3 ) 3 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar weight ratio of O is 2: 1. And then adding citric acid and ethylene glycol into the aqueous solution to form a mixed solution, wherein the molar ratio of each substance in the mixed solution is the sum of the metal elements contained in the catalyst: citric acid: ethylene glycol =1:1-1.5: 1-2. Heating the mixed solution at 60-90 deg.C for 5-20 hr until a viscous gel is obtained; the gel is then further heated to remove organic components, forming the precursor.
S3, synthesis of a perovskite type catalyst: and calcining the precursor obtained from the S2 at 800-1400 ℃ for 2-10 hours in an inert gas atmosphere. Ball-milling the powder obtained by calcination in an ethanol medium for 2-10 hours, drying, and then selecting sieves with different meshes to sieve to obtain the perovskite catalyst with the required size.
The invention also provides the application of the perovskite catalyst, the perovskite catalyst is used for preparing hydrogen peroxide by electrocatalytic reduction of oxygen, and the generation selectivity of the hydrogen peroxide is more than 50%.
Compared with the prior art, the invention has the beneficial effects that:
1. we find the Ln of the substance 2 NiO 4+δ Has the catalytic activity of producing hydrogen peroxide by electrocatalysis, can be used as a substitute of a noble metal catalyst, and greatly reduces the cost.
2. The perovskite catalyst prepared by the method of the invention is used for producing hydrogen peroxide through electrocatalysis, and has the characteristics of high efficiency and high selectivity.
Drawings
FIG. 1 shows Pr obtained in example 1 of the present invention 2 NiO 4+δ X-ray diffraction pattern of (a).
FIG. 2 shows Pr obtained in example 1 of the present invention 2 NiO 4+δ Scanning electron micrograph (c).
FIG. 3 shows Pr obtained in example 1 of the present invention 2 NiO 4+δ Transmission electron microscopy images and elemental analysis images of;
FIG. 4 shows Pr of application example 1 of the present invention 2 NiO 4+δ And (4) making an LSV curve of the hydrogen peroxide catalyst prepared by oxygen reduction.
FIG. 5 shows Pr of application example 1 of the present invention 2 NiO 4+δ The LSV curve obtained by preparing the hydrogen peroxide catalyst on the electrode of the rotating ring disk by oxygen reduction and the selectivity and the electron transfer number of the obtained electrocatalytic hydrogen peroxide are obtained.
FIG. 6 shows Pr in application example 1 of the present invention 2 NiO 4+δ The long-time preparation curve of the electrocatalytic hydrogen peroxide is shown.
Detailed Description
The invention is described in further detail below with reference to the following figures and detailed description:
example 1: preparation of perovskite catalyst Pr 2 NiO 4+δ
S1, preparing required materials: this example uses the nitrate as the water-soluble Pr salt, thus preparing Pr (NO) 3 ) 3 ·6H 2 O，Ni(NO 3 ) 2 ·6H 2 O, citric acid and ethylene glycol.
S2. Pr 2 NiO 4+δ Preparing a precursor: according to the chemical formula Pr of the target product 2 NiO 4+δ At medium stoichiometric ratio, 2 parts of Pr (NO) 3 ) 3 ·6H 2 O and 1 part of Ni (NO) 3 ) 2 ·6H 2 O is dissolved in deionized water to form an aqueous nitrate solution. It then adds citric acid and ethylene glycol to an aqueous nitrate solution at a final molar ratio of 1 part metal ions (including Pr ions and Ni ions), 1-1.5 parts citric acid, 1-2 parts ethylene glycol. The above solution is heated at 60-90 ℃ for 5-20 hours until a viscous gel is obtained. The gel is then further heated to remove organic components to give a precursor.
S3. Pr 2 NiO 4+δ The synthesis of (2): and calcining the precursor obtained from the S2 at 800-1400 ℃ for 2-10 hours in an inert gas atmosphere. Ball-milling the powder obtained by calcination in an ethanol medium for 2-10 hours, drying, selecting sieves with different meshes, and sieving to obtain the perovskite catalyst Pr with the required size 2 NiO 4+δ 。
Example 2: preparation of perovskite catalyst Pr 2-x La x NiO 4+δ
S1, preparing the required materials: pr (NO) 3 ) 3 ·6H 2 O，La(NO 3 ) 3 ·6H 2 O，Ni(NO 3 ) 2 ·6H 2 O, citric acid and ethylene glycol.
S2.Pr 2-x La x NiO 4+δ Preparing a precursor: according to the chemical formula Pr of the target product 2-x La x NiO 4+δ
In medium stoichiometric ratio, (2-x) parts of Pr (NO) 3 ) 3 ·6H 2 O, x part of La (NO) 3 ) 3 ·6H 2 O and 1 part of Ni (NO) 3 ) 2 ·6H 2 O is dissolved in deionized water to form an aqueous nitrate solution. Wherein the doping amount of La element in the final sample is La (NO) 3 ) 3 ·6H 2 The amount of O added, x, is controlled, in this example, by 0<x<2. Citric acid and ethylene glycol are then added to the aqueous nitrate solution at a final molar ratio of 1 part metal ion (including Pr, La and Ni ions), 1-1.5 parts citric acid, 1-2 parts ethylene glycol. Wherein the solution is heated at 60-90 ℃ for 5-20 hours until a viscous gel is obtained. The gel is then further heated to remove organic components to give a precursor.
S3. Pr 2-x La x NiO 4+δ The synthesis of (2): and calcining the precursor obtained from the S2 at 800-1400 ℃ for 2-10 hours in an inert gas atmosphere. Ball-milling the powder obtained by calcination in an ethanol medium for 2-10 hours, drying, selecting sieves with different meshes, and sieving to obtain the perovskite catalyst Pr with the required size 2-x La x NiO 4+δ 。
Example 3: preparation of perovskite catalyst Pr 2-x Nd x NiO 4+δ
S1, preparing required materials: pr (NO) 3 ) 3 ·6H 2 O，Nd(NO 3 ) 3 ·6H 2 O，Ni(NO 3 ) 2 ·6H 2 O, citric acid and ethylene glycol.
S2. Pr 2-x La x NiO 4+δ Preparing a precursor: according to the chemical formula Pr of the target product 2-x La x NiO 4+δ Medium stoichiometric ratio of Pr (NO) 3 ) 3 ·6H 2 O (2-x parts), Nd (NO) 3 ) 3 ·6H 2 O (x parts) and Ni (NO) 3 ) 2 ·6H 2 O (1 part) was dissolved in deionized water to form an aqueous nitrate solution. The doping amount of the Nd element in the final sample is Nd (NO) 3 ) 3 ·6H 2 The amount of O added, x, is controlled, in this example, by 0<x<2. Then the lemon is mixedCitric acid and ethylene glycol are added to an aqueous nitrate solution at a final molar ratio of 1 part metal ion (including Pr ion, Nd ion, and Ni ion), 1-1.5 parts citric acid, and 1-2 parts ethylene glycol. Wherein the solution is heated at 60-90 ℃ for 5-20 hours until a viscous gel is obtained. The gel is then further heated to remove organic components to give a precursor.
S3. Pr 2-x Nd x NiO 4+δ The synthesis of (2): and calcining the precursor obtained from the S2 at 800-1400 ℃ for 2-10 hours in an inert gas atmosphere. Ball-milling the powder obtained by calcination in an ethanol medium for 2-10 hours, drying, selecting sieves with different meshes, and sieving to obtain the perovskite catalyst Pr with the required size 2-x Nd x NiO 4+δ 。
Example 4: preparation of perovskite catalyst Pr 2-x-y La x Nd y NiO 4+δ
S1, preparing required materials: pr (NO) 3 ) 3 ·6H 2 O，La(NO 3 ) 3 ·6H 2 O, Nd(NO 3 ) 3 ·6H 2 O，Ni(NO 3 ) 2 ·6H 2 O, citric acid and ethylene glycol.
S2. Pr 2-x-y La x Nd y NiO 4+δ Preparing a precursor: adding Pr (NO) according to the stoichiometric ratio in the chemical formula of the target product 3 ) 3 ·6H 2 O (2-x-y parts), La (NO) 3 ) 3 ·6H 2 O (x parts), Nd (NO) 3 ) 3 ·6H 2 O (y parts) and Ni (NO) 3 ) 2 ·6H 2 O (1 part) was dissolved in deionized water to form an aqueous nitrate solution. The doping amount of La and Nd elements in the final sample is defined by La (NO) 3 ) 3 ·6H 2 O and Nd (NO) 3 ) 3 ·6H 2 The amounts of added O, x and y, were controlled separately, and in this example, 0 was used<x<2、0<y<2 and 0<x+y<2. Citric acid and ethylene glycol are then added to an aqueous nitrate solution having a final molar ratio of 1 part metal ion (including Pr ion, La ion, Nd ion, and Ni ion), 1-1.5 parts citric acid1-2 parts of ethylene glycol. Wherein the solution is heated at 60-90 ℃ for 5-20 hours until a viscous gel is obtained. The gel is then further heated to remove organic components to give a precursor.
S3. Pr 2-x-y La x Nd y NiO 4+δ The synthesis of (2): and calcining the precursor obtained from the S2 at 800-1400 ℃ for 2-10 hours in an inert gas atmosphere. Ball-milling the powder obtained by calcination in an ethanol medium for 2-10 hours, drying, selecting sieves with different meshes, and sieving to obtain the perovskite catalyst Pr with the required size 2-x-y La x Nd y NiO 4+δ 。
XRD (X-ray diffraction) tests are carried out on the perovskite type catalyst prepared in each example, and the test result shows that the perovskite type catalyst prepared in each example has a single Ruddlesden-Popper phase structure and is high in purity. FIG. 1 shows Pr obtained in example 1 of the present invention 2 NiO 4+δ X-ray diffraction pattern of (Pr) 2 NiO 4+δ Expressed as Ruddlesden-Popper phase structure, the characteristic peaks at 24.28 °, 28.64 °, 31.74 °, 32.82 °, 33.22 ° and 47.38 ° respectively correspond to the orthogonal Pr of the space group Fmmm (# 69) 2 NiO 4 The (111), (004), (113), (200), (020) and (200) planes of (JCPDS PDF # 86-0870) are consistent; the purity of the material phase proved to be high.
The perovskite type catalyst prepared in the above examples was subjected to SEM test, and Pr obtained in example 1 is shown in FIG. 2 2 NiO 4+δ The scanning electron microscope image of (A) shows that the prepared perovskite catalyst particles are uniform, the particle size of a single particle is about 1-5 mu m, a plurality of particles are aggregated into large particles of about 10 mu m, and the surfaces of the particles are completely flat. The morphology of the perovskite type catalyst prepared by each example is equivalent to that of the attached figure 2.
The perovskite-type catalysts prepared in the above examples were subjected to TEM test and elemental analysis. Pr as shown in figure 3 for example 1 2 NiO 4+δ Transmission electron microscopy images and elemental analysis images of; the microstructure of the catalyst was studied by aberration-corrected high angle annular dark field imaging scanning transmission electron microscope (HAADF-STEM) andan atomic resolution HAADF-STEM survey was conducted. FIG. 3 (a) shows Pr obtained in example 1 2 NiO 4+δ Energy dispersive X-ray spectroscopy (EDS) of the particles, as seen at Pr 2 NiO 4+δ No elemental segregation was observed in the particles, several elements were homogeneously distributed. From FIG. 3 (b), Pr 2 NiO 4+δ Nanoparticle edge [111 ]]High resolution scanning transmission electron microscope (HR-STEM) images of the zone axis can be observed. Wherein the upper inset in the diagram (b) of FIG. 3 is a Fast Fourier Transform (FFT) image of the diagram (b) of FIG. 3, (1-10) Pr 2 NiO 4+δ The reflection surface of (b) is denoted as a lower illustration image in fig. 3 (b). The corresponding atomic model with the same projection view is shown in fig. 3 (c). These further confirm the single phase structure of the perovskite-type catalyst prepared by the present invention.
Application example 1:
the perovskite catalyst prepared in each embodiment is used for preparing hydrogen peroxide by electrocatalytic reduction of oxygen. Pr obtained in example 1 was used in this application example 2 NiO 4+δ As a catalyst, the oxygen is reduced by electrocatalysis to prepare hydrogen peroxide.
Monitoring the process of preparing hydrogen peroxide, as shown in figures 4 and 5, Pr was measured 2 NiO 4+δ LSV curve and Pr of catalyst for preparing hydrogen peroxide by oxygen reduction 2 NiO 4+δ The LSV curve obtained by preparing the hydrogen peroxide catalyst on the electrode of the rotating ring disk by oxygen reduction and the selectivity and the electron transfer number of the obtained electrocatalytic hydrogen peroxide are obtained. As can be seen from FIG. 4, two regions of decreasing LSV curves are clearly observed, the first of which is the 2 electron reaction path which reaches the limiting current of about 2.75 mA cm at 0.3V to 0.6V directly -2 (ii) a After 0.6V, the 4 electron reaction path was entered. The hydrogen peroxide generation can also be monitored on the ring electrode from FIG. 5, where Pr is 2 NiO 4+δ The generating selectivity of the hydrogen peroxide can reach more than 50 percent. The LSV curve on the disk electrode and the corresponding electron transfer number were about 2, confirming the two-electron oxygen reduction electrocatalytic reaction that was performed.
FIG. 6 shows Pr in the present application 2 NiO 4+δ Long-term (0-24 hours) stability curve of electrocatalytic hydrogen peroxide. In 0.10M KOH electrolyte and 10 mA cm -2 Pr at Current Density 2 NiO 4+δ The catalyst exhibits good stability over a long period of time. Finally, limit H 2 O 2 The concentration can be determined to be 0.24 mM.
What has been described above is only a few embodiments of the present invention. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (9)
1. A perovskite-type catalyst for two-electron oxygen reduction electrocatalysis, characterized in that: the perovskite catalyst has a chemical formula Ln 2 NiO 4+δ Wherein Ln is selected from one or more of rare earth metal elements La, Pr or Nd; wherein the stoichiometric ratio of the sum of the stoichiometric ratios of the rare earth metal elements to Ni is 2: 1.
2. The perovskite-type catalyst for two-electron oxygen reduction electrocatalysis according to claim 1, characterized in that: the perovskite-type catalyst has a Ruddlesden-Popper phase structure.
3. The perovskite-type catalyst for two-electron oxygen reduction electrocatalysis according to claim 2, characterized in that: the perovskite type catalyst is micron particles, the particles are uniform, the average particle size of a single particle is 1-5 mu m, the surface of the particle is flat, elements in the particle are uniformly distributed, the phenomenon of element segregation is not observed, and a plurality of particles are aggregated into large particles with the average particle size of 10 mu m.
4. A process for preparing a perovskite-type catalyst for two-electron oxygen reduction electrocatalysis according to any one of claims 1 to 3, characterized in that it comprises the following steps:
s1: preparing a desired material comprising: one or more of water-soluble rare earth metal salts, citric acid, ethylene glycol and Ni (NO) 3 ) 2 ·6H 2 O；
Wherein the rare earth metal is selected from one or more of La, Pr or Nd;
s2, preparation of a precursor: mixing the water-soluble rare earth metal salt and Ni (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water to form an aqueous solution; wherein the rare earth metal salt and Ni (NO) 3 ) 2 ·6H 2 O is added according to the stoichiometric ratio of each rare earth metal element and Ni in the chemical formula of the target product, namely the perovskite catalyst; then adding citric acid and ethylene glycol into the aqueous solution to form a mixed solution; heating the mixed solution to obtain viscous gel; further heating the gel to remove organic components to form the precursor;
s3, synthesis of a perovskite type catalyst: calcining the precursor obtained in the step S2 in an inert gas atmosphere, and ball-milling and drying the calcined powder in an ethanol medium to obtain the perovskite catalyst.
5. The method of preparing a perovskite-type catalyst for two-electron oxygen reduction electrocatalysis according to claim 4, characterized in that: wherein the water-soluble rare earth metal salt is selected from one or more of nitrate, acetate and sulfate of rare earth metal elements La, Pr or Nd.
6. The method of preparing a perovskite-type catalyst for two-electron oxygen reduction electrocatalysis according to claim 4, characterized in that: the mixed solution in step S2 is heated at 60-90 deg.C for 5-20 hr.
7. The method of preparing a perovskite-type catalyst for two-electron oxygen reduction electrocatalysis according to claim 4, characterized in that: in step S2, the molar ratio of each substance in the mixed solution is the sum of the metal elements contained in the perovskite-type catalyst, citric acid to ethylene glycol =1:1-1.5: 1-2.
8. The method of preparing a perovskite-type catalyst for two-electron oxygen reduction electrocatalysis according to claim 4, characterized in that: in step S3, the calcination temperature is 800-1400 ℃ and the calcination time is 2-10 hours.
9. Use of a perovskite-type catalyst for two-electron oxygen reduction electrocatalysis according to any of claims 1 to 3, characterized in that: the perovskite catalyst is used for preparing hydrogen peroxide by electrocatalytic reduction of oxygen, and the generation selectivity of the hydrogen peroxide is more than 50%.
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