CN114875432B - 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 29
- 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
- 230000009467 reduction Effects 0.000 title claims abstract description 25
- 239000010411 electrocatalyst Substances 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 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
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract 4
- 239000002245 particle Substances 0.000 claims description 26
- 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
- 239000000463 material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 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 4
- 229910002828 Pr(NO3)3·6H2O Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 229910003205 Nd(NO3)3·6H2O Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25B1/30—Peroxides
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- 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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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application discloses a perovskite catalyst for di-electron oxygen reduction electro-catalysis, 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 application also provides a preparation method of the catalyst, which comprises the following steps: 1) Water-soluble rare earth metal salt and Ni (NO 3 ) 2 6H2O is 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 a high temperature in an inert gas atmosphere, ball-milling and drying the calcined product to obtain the catalyst. The perovskite catalyst provided by the application is used for preparing hydrogen peroxide by electrocatalytic reduction of oxygen, and the generation selectivity of hydrogen peroxide is more than 50%.
Description
Technical Field
The application 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 productThe product has wide application, including medical, military and industrial application, such as disinfection, waste water treatment, chemical synthesis, etc. The main method for preparing hydrogen peroxide industrially at present is a 2-ethyl anthraquinone method, which has high energy consumption, complex process and high cost. In contrast, H is prepared by a two-electron electrochemical oxygen reduction reaction process using a simple electrochemical device 2 O 2 Can effectively avoid H 2 O 2 Realize H 2 O 2 Is now available, is a novel H with low energy consumption, low manufacturing cost and high safety 2 O 2 Synthesis technology. However, there is still a lack of electrocatalysts with high catalytic performance and low cost.
Although noble metals and alloys thereof, for H 2 O 2 Electrochemical preparation has high selectivity. However, the high cost and rarity of precious metal components makes future large-scale deployment challenging. Thus, more and more researchers are looking at non-noble metal catalysts. Perovskite-like catalysts are used as catalysts for a variety of electrochemical reactions due to their physical and chemical properties. The catalyst has the advantages of low cost, high stability of crystal structure, ingenious flexibility of catalyst design and the like. However, perovskite catalysts are used for electrocatalytic reduction of oxygen (O 2 ) Preparation of hydrogen peroxide (H) 2 O 2 ) Is not reported yet.
Disclosure of Invention
Based on the prior art, the application aims to provide a perovskite catalyst and a preparation method thereof, wherein 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 object, the present application adopts the following technical scheme.
The application firstly provides a perovskite catalyst for di-electron oxygen reduction electro-catalysis, which has a Ruddlesden-Popper phase structure and has a chemical formula as follows: ln (Ln) 2 NiO 4+δ Wherein Ln is one or more of rare earth metal elements La, pr or Nd; wherein the rare earth metal elementThe stoichiometric ratio of the sum to Ni is 2:1, e.g. PrLaNiO 4+δ 。
Further, the perovskite catalyst is micron particles, the particles are uniform, the average particle diameter of single particles is 1-5 mu m, the particle surfaces are 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 application 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 rare earth metal salts soluble in water, citric acid, ethylene glycol and Ni (NO 3 ) 2 ·6H 2 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, for example: preparation of perovskite catalyst Pr 2 NiO 4+δ Nitrate Pr (NO) 3 ) 3 ·6H 2 O; preparation of PrLaNiO 4+δ Nitrate Pr (NO) 3 ) 3 ·6H 2 O and La (NO) 3 ) 3 ·6H 2 O）、Ni(NO 3 ) 2 ·6H 2 O）。
S2, preparing a precursor: the rare earth metal salt and Ni (NO 3 ) 2 ·6H 2 O is dissolved 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 element to Ni in the chemical formula of the target product, namely the perovskite type catalyst; for example, pr is the target product 2 NiO 4+δ Pr (NO) can be added 3 ) 3 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O was 2:1. Then adding citric acid and ethylene glycol into the aqueous solution to form a mixed solution, wherein the molar ratio of substances in the mixed solution is the sum of metal elements contained in the catalyst: citric acid: ethylene glycol=1:1-1.5:1-2. Mixing the above materialsHeating the solution at 60-90 ℃ for 5-20 hours until a viscous gel is obtained; the gel is then further heated to remove the organic components, forming the precursor.
S3, synthesizing a perovskite catalyst: calcining the precursor obtained in the step S2 for 2-10 hours at 800-1400 ℃ in an inert gas atmosphere. Ball milling the calcined powder in ethanol medium for 2-10 hr, drying, and sieving with different mesh sieves to obtain perovskite catalyst of required size.
The application also provides 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 application has the beneficial effects that:
1. we find out the kind of Ln for the first time 2 NiO 4+δ Has the catalytic activity of producing hydrogen peroxide by electrocatalytic reaction, can be used as a substitute of noble metal catalyst, and greatly reduces the cost.
2. The perovskite catalyst prepared by the method has the characteristics of high efficiency and high selectivity in electrocatalytic production of hydrogen peroxide.
Drawings
FIG. 1 shows Pr obtained in example 1 of the present application 2 NiO 4+δ X-ray diffraction pattern of (c).
FIG. 2 shows Pr obtained in example 1 of the present application 2 NiO 4+δ Is a scanning electron microscope image of (1).
FIG. 3 shows Pr obtained in example 1 of the present application 2 NiO 4+δ Transmission electron microscopy images and elemental analysis images;
FIG. 4 shows Pr of application example 1 of the present application 2 NiO 4+δ And (3) taking the LSV curve as an LSV curve for preparing the hydrogen peroxide catalyst by oxygen reduction.
FIG. 5 shows Pr of application example 1 of the present application 2 NiO 4+δ LSV curve obtained by preparing hydrogen peroxide catalyst on rotating ring plate electrode by oxygen reduction and selectivity and electron transfer number of electrocatalytic hydrogen peroxide.
FIG. 6 shows Pr of application example 1 of the present application 2 NiO 4+δ Is to be controlled by the electric catalystAnd (5) preparing a curve for a long time by dissolving hydrogen peroxide.
Detailed Description
The application is described in further detail below with reference to the attached drawings and detailed description:
example 1: preparation of perovskite catalyst Pr 2 NiO 4+δ
S1, preparing required materials: the water-soluble Pr salt of this example was nitrate, 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 In stoichiometric ratio, 2 parts Pr (NO 3 ) 3 ·6H 2 O and 1 part of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in deionized water to form an aqueous nitrate solution. Which is then added to an aqueous nitrate solution with 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 was heated at 60-90 ℃ for 5-20 hours until a viscous gel was obtained. The gel is then further heated to remove the organic components to obtain the precursor.
S3. Pr 2 NiO 4+δ Is synthesized by the following steps: calcining the precursor obtained in the step S2 for 2-10 hours at 800-1400 ℃ in an inert gas atmosphere. Ball milling the calcined powder in ethanol medium for 2-10 hr, drying, sieving with different mesh sieve to obtain perovskite catalyst Pr with required size 2 NiO 4+δ 。
Example 2: preparation of perovskite catalyst Pr 2-x La x NiO 4+δ
S1, preparing 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 Precursor preparationThe preparation method comprises the following steps: according to the chemical formula Pr of the target product 2-x La x NiO 4+δ
In stoichiometric ratio, pr (2-x) part (NO 3 ) 3 ·6H 2 O, x parts of La (NO) 3 ) 3 ·6H 2 O and 1 part of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in deionized water to form an aqueous nitrate solution. Wherein the doping amount of La element in the final sample is represented by La (NO 3 ) 3 ·6H 2 The O addition amount x is controlled, and in this embodiment, 0 is used<x<2. The citric acid and ethylene glycol were then added to an aqueous nitrate solution having a final molar ratio of 1 part metal ions (including Pr ions, la ions, and Ni ions), 1-1.5 parts citric acid, 1-2 parts ethylene glycol. Wherein 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 the organic components to obtain the precursor.
S3. Pr 2-x La x NiO 4+δ Is synthesized by the following steps: calcining the precursor obtained in the step S2 for 2-10 hours at 800-1400 ℃ in an inert gas atmosphere. Ball milling the calcined powder in ethanol medium for 2-10 hr, drying, sieving with different mesh sieve to obtain perovskite catalyst Pr with 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 In stoichiometric ratio, 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) is dissolved in deionized water to form an aqueous nitrate solution. Wherein the doping amount of Nd element in the final sample is represented by Nd (NO 3 ) 3 ·6H 2 The O addition amount x is controlled, and in this embodiment, 0 is used<x<2. Citric acid and ethylene glycol were then added to an aqueous nitrate solution having a final molar ratio of 1 part metal ions (including Pr ions, nd ions, and Ni ions), 1-1.5 parts citric acid, and 1-2 parts ethylene glycol. Wherein 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 the organic components to obtain the precursor.
S3. Pr 2-x Nd x NiO 4+δ Is synthesized by the following steps: calcining the precursor obtained in the step S2 for 2-10 hours at 800-1400 ℃ in an inert gas atmosphere. Ball milling the calcined powder in ethanol medium for 2-10 hr, drying, sieving with different mesh sieve to obtain perovskite catalyst Pr with 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: pr (NO 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. Wherein the doping amount of La and Nd elements in the final sample is represented by La (NO 3 ) 3 ·6H 2 O and Nd (NO) 3 ) 3 ·6H 2 The O addition amounts x and y are controlled separately, in this embodiment 0 is used<x<2、0<y<2 and 0<x+y<2. Subsequently lemon is addedThe acid and glycol are added to an aqueous nitrate solution with a final molar ratio of 1 part metal ions (including Pr ions, la ions, nd ions, and Ni ions), 1-1.5 parts citric acid, and 1-2 parts glycol. Wherein 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 the organic components to obtain the precursor.
S3. Pr 2-x-y La x Nd y NiO 4+δ Is synthesized by the following steps: calcining the precursor obtained in the step S2 for 2-10 hours at 800-1400 ℃ in an inert gas atmosphere. Ball milling the calcined powder in ethanol medium for 2-10 hr, drying, sieving with different mesh sieve to obtain perovskite catalyst Pr with required size 2-x-y La x Nd y NiO 4+δ 。
XRD tests are carried out on the perovskite type catalysts prepared in the examples, and the test results show that the perovskite type catalysts prepared in the examples have a single Ruddlesden-Popper phase structure and are high in purity. As shown in FIG. 1, pr obtained in example 1 of the present application 2 NiO 4+δ X-ray diffraction pattern, pr 2 NiO 4+δ Characteristic peaks at 24.28 °, 28.64 °, 31.74 °, 32.82 °, 33.22 ° and 47.38 ° respectively, are orthogonal Pr to the space group Fmmm (# 69) expressed as Ruddlesden-Popper phase structure 2 NiO 4 The (111), (004), (113), (200), (020) and (200) planes of (JCPCDS PDF#86-0870) are identical; the purity of the material phase was proved to be high.
SEM test of perovskite catalyst prepared in each of the above examples was carried out, as shown in FIG. 2 for Pr prepared in example 1 2 NiO 4+δ The scanning electron microscope image of the perovskite catalyst particles can be seen, the prepared perovskite catalyst particles are uniform, the particle size of single particles is about 1-5 mu m, a plurality of particles are aggregated into large particles with the particle size of about 10 mu m, and the particle surfaces are completely flat. The morphology of the perovskite type catalyst prepared by each example is equivalent to that of fig. 2.
TEM tests and elemental analyses were performed on the perovskite-type catalysts prepared in the above examples. As shown in FIG. 3, pr obtained in example 1 2 NiO 4+δ Transmission electron microscopy images and elemental analysis images; the microstructure of the catalyst was studied by aberration-correcting high-angle annular dark field imaging transmission electron microscopy (HAADF-STEM), and atomic resolution HAADF-STEM investigation was also performed. As shown in FIG. 3 (a), pr obtained in example 1 2 NiO 4+δ Energy dispersive X-ray spectroscopy (EDS) of particles, seen at Pr 2 NiO 4+δ No element segregation was observed in the particles and several elements were uniformly distributed. From the graph (b) of FIG. 3, 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 FIG. 3 (b) is the Fast Fourier Transform (FFT) image of FIG. 3 (b), (1-10) Pr 2 NiO 4+δ Is marked as the 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 application.
Application example 1:
the perovskite catalyst prepared in each embodiment is used for preparing hydrogen peroxide by electrocatalytic reduction of oxygen. The present application example uses Pr obtained in example 1 2 NiO 4+δ As a catalyst, electrocatalytic reduction of oxygen is adopted to prepare hydrogen peroxide.
Monitoring the hydrogen peroxide preparation process, as shown in figures 4 and 5, pr respectively 2 NiO 4+δ LSV curve and Pr for preparing hydrogen peroxide catalyst by oxygen reduction 2 NiO 4+δ LSV curve obtained by preparing hydrogen peroxide catalyst on rotating ring plate electrode by oxygen reduction and selectivity and electron transfer number of electrocatalytic hydrogen peroxide. As can be seen from FIG. 4, the two-step down region of the LSV curve is clearly observed, wherein the first region is a 2 electron reaction path which reaches a limiting current directly at 0.3V-0.6V, about 2.75 mA cm -2 The method comprises the steps of carrying out a first treatment on the surface of the After 0.6V, the reaction proceeds to the 4-electron reaction path. The hydrogen peroxide formation can also be monitored on the ring electrode from FIG. 5, where Pr 2 NiO 4+δ The generation selectivity of hydrogen peroxide can reach more than 50 percent. DiskThe LSV curve and corresponding electron transfer number on the electrode were about 2, confirming the two electron oxygen reduction electrocatalytic reaction.
FIG. 6 is Pr in the present application 2 NiO 4+δ The stability profile of electrocatalytic hydrogen peroxide for a long period of time (0-24 hours). In 0.10M KOH electrolyte and 10 mA cm -2 Pr under current density condition 2 NiO 4+δ The catalyst exhibits good stability over time. Finally, limit H 2 O 2 The concentration may be determined to be 0.24 mM.
What has been described above is only a partial embodiment of the application. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the structure of the present application, and these should also be considered as the scope of the present application, which does not affect the effect of the implementation of the present application and the utility of the patent. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (9)
1. An application of a perovskite catalyst for di-electron oxygen reduction electrocatalysis, which is characterized in that: the perovskite catalyst is used for preparing hydrogen peroxide by electrocatalytic reduction of oxygen; wherein: the chemical formula of the perovskite catalyst is Ln 2 NiO 4+δ Wherein Ln is one or more of rare earth metal elements La, pr or Nd; wherein the stoichiometric ratio of the sum of the rare earth metal elements to Ni is 2:1.
2. Use of a perovskite catalyst for di-electron oxygen reduction electrocatalysis according to claim 1, wherein: the perovskite catalyst has a Ruddlesden-Popper phase structure.
3. Use of a perovskite catalyst for di-electron oxygen reduction electrocatalysis according to claim 2, wherein: the perovskite catalyst is micron particles, the particles are uniform, the average particle diameter of single particles is 1-5 mu m, the surfaces of the particles are flat, elements in the particles are uniformly distributed, no element segregation phenomenon is observed, and a plurality of particles are aggregated into large particles with the average particle diameter of 10 mu m.
4. Use of a perovskite catalyst for di-electron oxygen reduction electrocatalysis according to any one of claims 1 to 3, wherein the method of preparing the perovskite catalyst comprises the steps of:
s1: preparing a desired material, comprising: one or more of rare earth metal salts soluble in water, 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, preparing a precursor: combining the water-soluble rare earth metal salt with Ni (NO 3 ) 2 ·6H 2 O is dissolved 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 element to Ni in the chemical formula of the target product, namely the perovskite type 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, synthesizing a perovskite catalyst: calcining the precursor obtained in the step S2 in an inert gas atmosphere, ball-milling the calcined powder in an ethanol medium, and drying to obtain the perovskite catalyst.
5. The use of a perovskite catalyst for use in a two-electron oxygen reduction electrocatalyst according to claim 4, wherein: 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 use of a perovskite catalyst for use in a two-electron oxygen reduction electrocatalyst according to claim 4, wherein: the heating condition of the mixed solution in the step S2 is that the mixed solution is heated for 5 to 20 hours at the temperature of 60 to 90 ℃.
7. The use of a perovskite catalyst for use in a two-electron oxygen reduction electrocatalyst according to claim 4, wherein: the molar ratio of each substance in the mixed solution in the step S2 is the sum of metal elements contained in the perovskite catalyst, namely citric acid and ethylene glycol=1:1-1.5:1-2.
8. The use of a perovskite catalyst for use in a two-electron oxygen reduction electrocatalyst according to claim 4, wherein: in the step S3, the calcining temperature is 800-1400 ℃ and the calcining time is 2-10 hours.
9. Use of a perovskite catalyst for di-electron oxygen reduction electrocatalysis according to claim 1, wherein: the generation selectivity of hydrogen peroxide is more than 50%.
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