CN114990582A - Bimetal oxide OV-NiMnO 3 Micron ball and preparation method thereof - Google Patents
Bimetal oxide OV-NiMnO 3 Micron ball and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electrocatalysis, and provides a bimetal oxide OV-NiMnO rich in oxygen vacancy 3 A microsphere and its preparation method are provided. The preparation method comprises the following steps: s1, adding a nickel source compound, a manganese source compound and an organic compound into a mixed solution of deionized water and absolute ethyl alcohol, stirring, and carrying out hydrothermal reaction to obtain a Ni-Mn precursor; s2, transferring the Ni-Mn precursor into a tube furnace, oxidizing the precursor under the air environment condition, and naturally cooling the tube furnace to room temperature to obtain NiMnO 3 Micro-balls; s3, mixing NiMnO 3 Placing the microsphere sample in a tube furnace, pyrolyzing the microsphere sample under the condition of argon saturation, and obtaining the bimetal oxide OV-NiMnO rich in oxygen vacancy after the tube furnace is naturally cooled to room temperature 3 And (4) micro-spheres. The oxygen vacancy-rich gold provided by the inventionBelongs to oxide OV-NiMnO 3 The preparation method of the micron sphere has simple synthesis process and mild reaction condition, and the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared by the method 3 The reaction of the micron ball as the catalyst has high ammonia producing performance and high Faraday efficiency.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a bimetal oxide OV-NiMnO rich in oxygen vacancy 3 A microsphere and its preparation method are provided.
Background
In recent years, with the vigorous development of society, the use and consumption of fossil fuels are increasing, and the search for new energy substitutes is receiving wide attention in the energy field. Ammonia (NH) 3 ) As one of the important inorganic energy sources, it has advantages of high energy density, low pollution emission, and the like, and is also widely used as a raw material in the fields of resins, fertilizers, fuels, pharmaceuticals, and the like. At present, the method for artificially synthesizing ammonia gas is mainly to directly synthesize nitrogen and hydrogen under the conditions of high temperature and high pressure by a Haber-Bosch method, so that the method needs very harsh high-temperature and high-pressure environment and equipment support, and the method has high greenhouse gas emission, serious environmental pollution and is not beneficial to sustainable development. The electrocatalysis nitrogen reduction ammonia (E-NRR) overcomes the defects of the traditional Haber-Bosch method, can produce ammonia mildly and efficiently at normal temperature, meets the requirements of green chemistry, and has received extensive attention and research in recent years.
Although many researchers have demonstrated electrocatalytic N 2 Reduction synthesis of NH 3 Is feasible, but the activity and selectivity of most electrocatalysts remain at relatively low levels due to the constraints of the N ≡ N bond. Meanwhile, the main competitive reaction of HER as the e NRR greatly inhibits the synthesis of NH 3 The efficiency of (c). Thus increasing the catalyst pair N 2 While promoting the catalyst to N 2 The transfer of electrons to accelerate the N ≡ N cracking is the key to the preparation of high performance catalysts. Considering that it is extremely difficult to prepare a heterogeneous catalyst having a unique electron donating ability and excellent chemical stability, more active sites are introduced into the electrocatalyst to increase the p-N 2 Is extremely urgent and non-activeIt is often important. Introduction of oxygen vacancies, which are considered to be the most common anion vacancies in transition metal oxides due to their lower energy of formation, is a very effective improvement for oxide catalysts. Meanwhile, theoretically, the oxygen vacancy has important significance for enhancing the adsorption and activation of inert gas molecules and reducing the energy barrier of the reaction, so that the oxygen vacancy is introduced into the electrocatalyst and is used as a catalytic active center, and the oxygen vacancy can be used as an effective strategy for adjusting an electronic structure, reducing an activation energy barrier and further improving the activity of the E-NRR. According to previous reports, various oxide materials rich in oxygen vacancy have been prepared and applied to the electrocatalytic nitrogen reduction ammonia production, so as to achieve the purposes of improving the ammonia production performance, such as improving the yield and optimizing the reaction kinetics. For example, Zhang et al convert MnO by a simple self-pyrolysis process 2 The nano wire is pyrolyzed under the protection of argon at 350 ℃ in MnO 2 A large number of oxygen vacancies are formed on the surface of the nanowire (Ling Zhang, et al chem. MnO rich in oxygen vacancy prepared x The nano-wire has excellent electro-catalytic nitrogen reduction performance (ammonia yield: 9.97 mu g/h/cm) 2 Faraday efficiency: 11.4%) and original MnO 2 Comparison (Ammonia production: 1.41. mu.g/h/cm) 2 Faraday efficiency: 1.96%) had a large lift.
Compared with a single metal oxide, the double metal oxide has double metal sites, and can better fix nitrogen in the nitrogen reduction process to carry out the next ammonia production process. However, the research on the bimetallic oxide is rare, and the bimetallic oxide obtained by the research has complex synthesis process, high reaction condition requirement, low ammonia production performance of the bimetallic oxide and low Faraday efficiency.
Based on the above problems, the present invention provides a bimetallic oxide OV-NiMnO rich in oxygen vacancy 3 The preparation method of the micron sphere aims to solve the problems that the synthesis process of the bimetallic oxide is complex, the requirement on reaction conditions is high, the ammonia production performance of the reaction of the bimetallic oxide as a catalyst is low, and the Faraday efficiency is low.
Disclosure of Invention
To solve the existing bimetal oxideThe invention provides a bimetal oxide OV-NiMnO rich in oxygen vacancy, which has the problems of complex synthesis process, high requirement on reaction conditions, low ammonia production performance of the reaction using the bimetal oxide as a catalyst and low Faraday efficiency 3 A preparation method of micro-spheres.
The preparation method comprises the following steps:
s1, adding a nickel source compound, a manganese source compound and an organic compound into a mixed solution of deionized water and absolute ethyl alcohol, stirring, and then carrying out a hydrothermal reaction to obtain a Ni-Mn precursor;
s2, placing the Ni-Mn precursor into a tube furnace, oxidizing the precursor under the air environment condition, and naturally cooling the tube furnace to room temperature to obtain NiMnO 3 Micro-balls;
s3, mixing the NiMnO 3 Placing the micron spheres in the tube furnace, pyrolyzing the micron spheres under the condition of argon saturation, and obtaining the bimetal oxide OV-NiMnO rich in oxygen vacancy after the tube furnace is naturally cooled to room temperature 3 And (4) micro-spheres.
Optionally, in the step S1, the molar ratio of the nickel source compound, the manganese source compound, and the organic compound is 1:1:10, and the molar amount of the nickel source compound is 0.008 to 0.012 mol.
Optionally, the total volume of the mixed solution in the step S1 is 50-80 mL, and the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1.
optionally, the nickel source compound is nickel acetate tetrahydrate or nickel nitrate hexahydrate, the manganese source compound is manganese acetate tetrahydrate, and the organic compound is urea.
Optionally, in the step S1, the stirring temperature is 20 to 30 ℃, and the stirring time is 10 to 20 min.
Optionally, the temperature of the hydrothermal reaction in the step S1 is 150-180 ℃, and the reaction time is 5-7 hours.
Optionally, in the step S2, the oxidation temperature is 500-600 ℃, and the oxidation time is 2-3 hours.
Optionally, in the step S3, the pyrolysis temperature is 300-500 ℃, and the pyrolysis time is 2 hours.
Another object of the present invention is to provide an oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 And (4) micro-spheres.
The oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 The oxygen vacancy-rich bimetallic oxide OV-NiMnO as defined in any one of the above 3 A preparation method of the micron ball.
Optionally, said oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 The concentration value of oxygen vacancy in the microsphere is 21.5-32.2%.
The invention provides a bimetal oxide OV-NiMnO rich in oxygen vacancy 3 The preparation method of the micron sphere has simple synthesis process and mild reaction condition, and the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared by the method 3 The reaction of the micron ball as the catalyst has high ammonia producing performance and high Faraday efficiency.
Drawings
FIG. 1 is a view showing the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 Transmission electron microscope pictures of the microspheres;
FIG. 2 is an OV-NiMnO rich oxygen vacancy bimetallic oxide prepared in example 4 of the present invention 3 Scanning electron microscope pictures of the microspheres;
FIG. 3 is an OV-NiMnO rich oxygen vacancy bimetallic oxide prepared in example 4 of the present invention 3 XRD pattern of microspheres;
FIG. 4 is a graph of oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in example 1, example 2, example 3 and example 4 of the present invention 3 Graph comparing ESR of the microspheres;
FIG. 5 is a graph of oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in example 1, example 2, example 3 and example 4 of the present invention 3 XPS comparison of microspheres;
FIG. 6 is an OV-NiMnO rich oxygen vacancy bimetallic oxide prepared in example 4 of the present invention 3 When the microspheres are used as an electrocatalyst, the concentration of the catalyst is 5mVs in 0.1M KOH saturated with nitrogen and 0.1M KOH saturated with argon respectively -1 At a sweeping speed ofObtaining an LSV curve chart;
FIG. 7 is an oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 A performance diagram of ammonia yield and Faraday efficiency after testing under five groups of potentials when the microspheres are used as electrocatalysts;
FIG. 8 is a graph of oxygen vacancy rich bimetallic oxides OV-NiMnO prepared in examples 1, 2, 3 and 4 of the present invention 3 A performance comparison graph of ammonia yield and Faraday efficiency of reaction of the microspheres as a catalyst;
FIG. 9 shows the oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in example 4 of this invention 3 6 times of cycle performance test chart under-0.3V (relative to a standard hydrogen electrode) when the micron sphere is used as an electrocatalyst;
FIG. 10 shows the oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 And (3) a 20-hour i-t stability test chart when the micron spheres are used as an electrocatalyst.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments accompanied with figures are described in detail below, but the present invention is not to be construed as limiting the implementable range thereof.
Example 1
(1) 80mmol of urea is firstly dissolved in a mixed solution of 25mL of deionized water and 25mL of absolute ethyl alcohol, and stirred at 400rpm for 10min at 20 ℃. Then, 8mmol of NiC was added 4 H 6 O 4 ·4H 2 O and 8mmol of MnC 4 H 6 O 4 ·4H 2 O is added to the mixed solution and stirred for another 10 min. Finally, the solution was transferred to a stainless steel autoclave of polytetrafluoroethylene (total capacity 50mL) and kept at 150 ℃ for 5 h. After cooling to room temperature, the obtained Ni-Mn precursor was separated by centrifugation, washed with deionized water and ethanol, and finally dried in a vacuum drying oven.
(2) The synthesized Ni — Mn precursor was transferred to a tube furnace and oxidized in an air atmosphere. Specifically, Ni-Mn precursor is heated from room temperatureHeating to 500 deg.C and maintaining for 2h to obtain NiMnO 3 And (4) micro-spheres.
(3) Mixing 200mg of NiMnO 3 The micron balls are uniformly placed in a porcelain boat and transferred into a tube furnace for pyrolysis in an argon atmosphere. Specifically, NiMnO 3 Heating the micro-spheres from room temperature to 300 ℃ and keeping the temperature for 2 hours to obtain the oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 And (4) micro-spheres.
Example 2
(1) 90mmol of urea was first dissolved in 30mL of deionized water and 30mL of absolute ethanol and stirred at 400rpm for 10min at 25 ℃. Then, 9mmol of NiC was added 4 H 6 O 4 ·4H 2 O and 9mmol of MnC 4 H 6 O 4 ·4H 2 O was added to the solution and stirred for another 20 min. Finally, the solution was transferred to a stainless steel autoclave of polytetrafluoroethylene (total capacity 60mL) and kept at 160 ℃ for 7 h. After cooling to room temperature, the Ni-Mn precursor obtained by centrifugal separation is washed with deionized water and ethanol and finally dried in a vacuum drying oven.
(2) The synthesized Ni — Mn precursor was transferred to a tube furnace and oxidized in an air atmosphere. Specifically, the Ni-Mn precursor is heated to 550 ℃ from room temperature and is kept for 2h to obtain NiMnO 3 And (4) micro-spheres.
(3) 200mg of NiMnO 3 The micron balls are uniformly placed in a porcelain boat and transferred into a tube furnace for pyrolysis in an argon atmosphere. Specifically, NiMnO 3 Heating the micro-spheres from room temperature to 350 ℃, and keeping the temperature for 2 hours to obtain the oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 And (4) micro-spheres.
Example 3
(1) 100mmol of urea was first dissolved in 35mL of deionized water and 35mL of absolute ethanol and stirred at 400rpm for 10min at 30 ℃. Then, 10mmol of Ni (NO) 3 ) 2 ·6H 2 O and 10mmol of Mn (NO) 3 ) 2 ·6H 2 O was added to the solution and stirred for another 10 min. Finally, the solution was transferred to a stainless steel autoclave of polytetrafluoroethylene (total capacity 70mL),and kept at 170 ℃ for 6 h. After cooling to room temperature, the Ni-Mn precursor obtained by centrifugal separation is washed with deionized water and ethanol and finally dried in a vacuum drying oven.
(2) The synthesized Ni — Mn precursor was transferred to a tube furnace and oxidized in an air atmosphere. Specifically, the Ni-Mn precursor is heated to 550 ℃ from room temperature and is kept for 2h to obtain NiMnO 3 And (4) micro-spheres.
(3) Mixing NiMnO 3 The micron balls are uniformly placed in a porcelain boat and transferred into a tube furnace for pyrolysis in an argon atmosphere. Specifically, NiMnO 3 Heating the micro-spheres from room temperature to 400 ℃, and keeping the temperature for 2 hours to obtain the double metal oxide OV-NiMnO rich in oxygen vacancies 3 And (4) micro-spheres.
Example 4
(1) 120mmol of urea was first dissolved in 40mL of deionized water and 40mL of absolute ethanol and stirred at 400rpm for 10min at 30 ℃. Then, 12mmol of Ni (NO) 3 ) 2 ·6H 2 O and 12mmol of Mn (NO) 3 ) 2 ·6H 2 O was added to the solution and stirred for another 20 min. Finally, the solution was transferred to a stainless steel autoclave of polytetrafluoroethylene (total capacity 80mL) and kept at 180 ℃ for 7 h. After cooling to room temperature, the Ni-Mn precursor obtained by centrifugal separation is washed with deionized water and ethanol and finally dried in a vacuum drying oven.
(2) The synthesized Ni — Mn precursor was transferred to a tube furnace and oxidized in an air atmosphere. Specifically, the Ni-Mn precursor is heated to 600 ℃ from room temperature and is kept for 2h to obtain NiMnO 3 And (4) micro-spheres.
(3) Mixing NiMnO 3 The micron balls are uniformly placed in a porcelain boat and transferred into a tube furnace for pyrolysis in an argon atmosphere. Specifically, NiMnO 3 The microspheres were heated from room temperature to 500 ℃ and held for 2 h. Obtaining the bimetal oxide OV-NiMnO rich in oxygen vacancy 3 And (4) micro-spheres.
And (3) testing results:
in FIG. 1, a is an oxygen vacancy-rich bimetallic oxide O prepared in example 4 of this inventionV-NiMnO 3 Transmission electron microscope pictures of the microspheres; from the figure, OV-NiMnO can be known 3 The whole micron sphere has a spherical structure and NiMnO 3 The microspheres (shown as b in FIG. 1) have no significant structural change compared to the NiMnO due to the introduction of oxygen vacancies 3 The structure of (2) does not cause influence.
FIG. 2 a shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 Scanning electron microscope pictures of the microspheres; from the figure, OV-NiMnO can be known 3 The micro-spheres have a spherical structure with an irregular surface, and NiMnO 3 There was no significant structural change in the microspheres (as shown in b in fig. 2).
FIG. 3 is an OV-NiMnO rich oxygen vacancy bimetallic oxide prepared in example 4 of the present invention 3 XRD pattern of the microsphere, from which it can be seen that NiMnO was obtained 3 Microspheres and OV-NiMnO of example 4 3 The purity of the microspheres is higher and substantially coincides with standard cards.
FIG. 4 is a graph of oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in examples 1, 2, 3 and 4 of the present invention 3 Graph comparing ESR of the microspheres; from the figure, it can be seen that OV-NiMnO prepared in example 1, example 2, example 3 and example 4 3 The microspheres all showed a peak at g 2.003 indicating that oxygen vacancies were generated in all four samples prepared in the examples. And the peak strength increases with increasing pyrolysis temperature, indicating that increasing pyrolysis temperature can increase the number of oxygen vacancies.
FIG. 5 is a graph of oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in examples 1, 2, 3 and 4 of the present invention 3 XPS comparison of microspheres; it can be seen from the figure that OV-NiMnO prepared in example 1, example 2, example 3 and example 4 3 Oxygen element characteristic peak of the microsphere, wherein the peak positioned at 531.7eV represents an oxygen vacancy peak, and OV-NiMnO is obtained by calculating the fitted peak area 3 Concentration value of oxygen vacancy in microsphere, OV-NiMnO in example 1 3 The value of the concentration of oxygen vacancies in the microspheres was 21.5%, OV-NiMnO in example 2 3 Of oxygen vacancies in microspheresThe concentration value was 23.6%, OV-NiMnO in example 3 3 The value of concentration of oxygen vacancies in the microspheres was 25.4%, OV-NiMnO in example 4 3 The value of the concentration of oxygen vacancies in the microspheres was 32.2%. Illustrating the OV-NiMnO formation at different pyrolysis temperatures 3 The microsphere oxygen vacancy concentrations also varied, and the concentration of oxygen vacancies increased with increasing pyrolysis temperature.
FIG. 6 is an oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 The microspheres as catalyst were in a nitrogen-saturated electrolyte and an argon-saturated electrolyte at 5mVs, respectively -1 The LSV profile measured at the sweep rate of (c) shows that the LSV curve current measured in the nitrogen saturated electrolyte is greater than the current measured in the argon saturated electrolyte, indicating that nitrogen reduction to ammonia occurs in the nitrogen saturated electrolyte, indicating that the oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in example 4 3 The micron sphere has the electrocatalytic nitrogen reduction performance.
FIG. 7 shows the oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 The electrocatalytic nitrogen reduction performance of the microspheres is shown in the left graph, which is the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 3 Ammonia yields obtained at five sets of voltages with the microspheres used as catalyst. From the graph, it is understood that the maximum ammonia yield obtained at a voltage of-0.3V (relative to the standard hydrogen electrode) is 34.15. mu.g/h/mg cat . The right graph shows the faradaic efficiency obtained at five sets of voltages, and it is understood from the graph that the maximum faradaic efficiency obtained at a voltage of-0.1V (relative to a standard hydrogen electrode) is 14.5%.
FIG. 8 is a graph of oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in examples 1, 2, 3 and 4 of the present invention 3 Graph comparing ammonia production with faradaic efficiency for microspheres as catalyst; it can be seen from the figure that the pyrolysis temperature of different examples is different, and the concentration of oxygen vacancy is gradually increased along with the increase of the pyrolysis temperature, and the catalytic ammonia generating performance is also gradually increased.
FIG. 9 is an oxygen vacancy rich bimetallic oxidation made in example 4 of the present inventionObject OV-NiMnO 3 6 times of cycle performance test chart under-0.3V (relative to a standard hydrogen electrode) when the micron sphere is used as an electrocatalyst. From the figure, it can be seen that the oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in example 4 was subjected to six test runs 3 The ammonia yield and Faraday efficiency of the micron spheres as the electrocatalyst only slightly fluctuate without obvious performance degradation, which shows that the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 3 The performance repeatability of the microspheres is very excellent.
FIG. 10 is an oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 And (3) a 20-hour i-t stability test chart when the micron spheres are used as an electrocatalyst. It can be seen from the graph that the i-t curve tends to be flat in the 20 hour stability test, illustrating the oxygen vacancy rich bimetallic oxide OV-NiMnO prepared in example 4 3 The reaction of the microsphere as the electrocatalyst has excellent stability.
In conclusion, the oxygen vacancy-rich bimetallic oxide OV-NiMnO provided by the invention 3 The preparation method of the micron sphere has simple synthesis process, mild reaction condition and oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 The reaction with the micron balls as the catalyst has excellent performances of high ammonia yield and high Farad efficiency, and can be used for preparing ammonia by electrocatalysis nitrogen reduction, so that the electrochemical performance of preparing ammonia by electrocatalysis nitrogen reduction is obviously improved.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. Double-metal oxide OV-NiMnO rich in oxygen vacancy 3 The preparation method of the micron ball is characterized in that the packageThe method comprises the following steps:
s1, adding a nickel source compound, a manganese source compound and an organic compound into a mixed solution of deionized water and absolute ethyl alcohol, stirring, and then carrying out a hydrothermal reaction to obtain a Ni-Mn precursor;
s2, placing the Ni-Mn precursor into a tube furnace, oxidizing the precursor under the air environment condition, and naturally cooling the tube furnace to room temperature to obtain NiMnO 3 Micro-balls;
s3, mixing the NiMnO 3 Placing the micron spheres in the tube furnace, pyrolyzing the micron spheres under the condition of argon saturation, and obtaining the bimetal oxide OV-NiMnO rich in oxygen vacancy after the tube furnace is naturally cooled to room temperature 3 And (4) micro-spheres.
2. The oxygen vacancy-rich bimetallic oxide OV-NiMnO of claim 1 3 The method for preparing the microspheres is characterized in that the molar ratio of the nickel source compound to the manganese source compound to the organic compound in the step S1 is 1:1:10, and the molar weight of the nickel source compound is 0.008 to 0.012 mol.
3. The oxygen vacancy-rich bimetallic oxide OV-NiMnO of claim 1 3 The preparation method of the microspheres is characterized in that the total volume of the mixed solution in the step S1 is 50-80 mL, and the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1.
4. the oxygen vacancy-rich bimetallic oxide OV-NiMnO of claim 1 3 The preparation method of the microspheres is characterized in that the nickel source compound is nickel acetate tetrahydrate or nickel nitrate hexahydrate, the manganese source compound is manganese acetate tetrahydrate, and the organic compound is urea.
5. The oxygen vacancy-rich bimetallic oxide OV-NiMnO of claim 1 3 The preparation method of the micro-spheres is characterized in that in the step S1, the stirring temperature is 20-30 ℃, and the stirring time is 10-20 min.
6. The oxygen vacancy rich bimetallic oxide OV-NiMnO of claim 1 3 The preparation method of the microspheres is characterized in that the temperature of the hydrothermal reaction in the step S1 is 150-180 ℃, and the reaction time is 5-7 h.
7. The oxygen vacancy-rich bimetallic oxide OV-NiMnO of claim 1 3 The preparation method of the microspheres is characterized in that in the step S2, the oxidation temperature is 500-600 ℃, and the oxidation time is 2-3 h.
8. The oxygen vacancy-rich bimetallic oxide OV-NiMnO of claim 1 3 The preparation method of the microspheres is characterized in that the pyrolysis temperature in the step S3 is 300-500 ℃, and the pyrolysis time is 2 hours.
9. Double-metal oxide OV-NiMnO rich in oxygen vacancy 3 Microspheres of the double metal oxide OV-NiMnO rich in oxygen vacancies according to any of claims 1 to 8 3 A preparation method of the micron ball.
10. The oxygen vacancy rich bimetallic oxide OV-NiMnO of claim 9 3 The micron sphere is characterized in that the oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 The concentration value of oxygen vacancy in the microsphere is 21.5-32.2%.
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