CN114990582B - Bimetal oxide OV-NiMnO 3 Microsphere and preparation method thereof - Google Patents
Bimetal oxide OV-NiMnO 3 Microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electrocatalysis, and provides a bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 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 performing hydrothermal reaction to obtain a Ni-Mn precursor; s2, transferring the Ni-Mn precursor into a tube furnace and oxidizing under the air environment condition, and naturally cooling the tube furnace to room temperature to obtain NiMnO 3 A microsphere; s3, niMnO is carried out 3 Placing the microsphere sample in a tubular furnace and pyrolyzing under the condition of argon saturation, and naturally cooling the tubular furnace to room temperature to obtain the bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 And (3) microspheres. The invention provides a bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 The preparation method of the microspheres has simple synthesis process and mild reaction conditions, and the bimetallic oxide OV-NiMnO rich in oxygen vacancies prepared by the method 3 The reaction ammonia production performance of the microsphere as a catalyst is high, and the Faraday efficiency is high.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, in particular to a bimetallic oxide OV-NiMnO which is rich in oxygen vacancies 3 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 a great deal of attention in the energy field. Ammonia (NH) 3 ) As one of important inorganic energy sources, the material has the advantages of high energy density, low pollution emission, and the like, and is widely applied to the fields of resin, fertilizer, fuel, medicine, and the like as raw materials. At present, the method for artificially synthesizing ammonia 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 strict high temperature and high pressure environment and equipment support, has high emission of greenhouse gases, serious environmental pollution and is unfavorable for sustainable development. The method for preparing ammonia (E-NRR) by electrocatalytic nitrogen reduction overcomes the defects of the traditional Haber-Bosch method, can produce ammonia at normal temperature mildly and efficiently, meets the requirements of green chemistry, and has been widely focused and studied in recent years.
Although many researchers have demonstrated electrocatalytic N 2 Reduction synthesis of NH 3 It is possible but the activity and selectivity of most electrocatalysts remain at relatively low levels due to the restriction by the n≡n bond. While HER as the primary competing reaction for eNRR largely inhibits NH synthesis 3 Is not limited to the above-described embodiments. Thus increasing the catalyst to N 2 At the same time promote the adsorption capacity of the catalyst to N 2 Transferring electrons and thus accelerating the n≡n cleavage is critical for the preparation of high performance catalysts. Given that it is extremely difficult to prepare heterogeneous catalysts with 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 very important. The introduction of oxygen vacancies, which are considered the most common anion vacancies in transition metal oxides due to their lower energy of formation, is a very effective improved process for oxide catalysts. In theory, 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 the electronic structure, reducing the activation energy barrier and further improving the E-NRR activity. According to previous reports, various oxide materials rich in oxygen vacancies have been prepared for the electrocatalytic nitrogen reduction to ammonia for the purpose of improving ammonia production performance such as yield and optimizing reaction kinetics. For example, zhang et al carried out MnO by a simple self-pyrolysis method 2 Argon protection strip for nanowire at 350 DEG CPyrolysis under the member, at MnO 2 The nanowire surface is structured with a large number of oxygen vacancies (Ling Zhang, et al chem. Commun,2019,55,4627). Prepared MnO rich in oxygen vacancy x The nanowires have excellent electrocatalytic nitrogen reduction performance (ammonia yield: 9.97. Mu.g/h/cm) 2 Faraday efficiency: 11.4%) with the original MnO 2 Compared (ammonia yield: 1.41. Mu.g/h/cm) 2 Faraday efficiency: 1.96%) is greatly improved.
Compared with single metal oxide, the double metal oxide has double metal sites, and can fix nitrogen in the nitrogen reduction process better to carry out the next ammonia production process. However, the studies on the bimetallic oxide are very rare, and the synthesis process of the bimetallic oxide obtained by the studies is complex, the requirements on reaction conditions are high, the ammonia production performance of the bimetallic oxide is low, and the Faraday efficiency is low.
Based on the above problems, the present invention provides a bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 The preparation method of the microspheres solves the problems of complex synthesis process of the bimetallic oxide, high requirement on reaction conditions, low ammonia production performance of the reaction of the bimetallic oxide as a catalyst and low Faraday efficiency.
Disclosure of Invention
In order to solve the problems of complex synthesis process, high requirement on reaction conditions, low ammonia production performance in the reaction by taking the bimetallic oxide as a catalyst and low Faraday efficiency of the conventional bimetallic oxide, the invention provides the bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 A preparation method of microspheres.
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 performing hydrothermal reaction to obtain a Ni-Mn precursor;
s2, placing the Ni-Mn precursor into a tube furnace and oxidizing under the air environment condition, and naturally cooling the tube furnace to room temperature to obtain NiMnO 3 A microsphere;
s3, mixing the NiMnO 3 The microspheres are placed on the tube typePyrolyzing in a furnace under the condition of argon saturation, and naturally cooling the tubular furnace to room temperature to obtain the bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 And (3) microspheres.
Optionally, in the step S1, the molar ratio of the nickel source compound to the manganese source compound to the organic compound is 1:1:10, and the molar amount of the nickel source compound is 0.008-0.012 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 ethanol 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 20-30 ℃ and the stirring time is 10-20 min.
Optionally, the temperature of the hydrothermal reaction in the step S1 is 150-180 ℃, and the reaction time is 5-7 h.
Optionally, the oxidation temperature in the step S2 is 500-600 ℃, and the oxidation time is 2-3 h.
Optionally, the pyrolysis temperature in the step S3 is 300-500 ℃, and the pyrolysis time is 2h.
Another object of the present invention is to provide a bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 And (3) microspheres.
The oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 The oxygen vacancy-rich bimetallic oxide OV-NiMnO of any one of the preceding claims 3 The preparation method of the microspheres.
Optionally, the oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 The concentration value of oxygen vacancies in the microspheres is 21.5% -32.2%.
The invention provides a bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 The preparation method of the microspheres has simple synthesis process and mild reaction conditions, and the bimetallic oxide OV-NiMnO rich in oxygen vacancies prepared by the method 3 Microsphere as catalystThe reaction ammonia production performance is high, and the Faraday efficiency is high.
Drawings
FIG. 1 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO obtained in example 4 of the present invention 3 Transmission electron microscope pictures of the microspheres;
FIG. 2 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO obtained in example 4 of the present invention 3 Scanning electron microscope pictures of the microspheres;
FIG. 3 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 XRD pattern of microspheres;
FIG. 4 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO produced in examples 1, 2, 3 and 4 of the present invention 3 ESR contrast plot of microspheres;
FIG. 5 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO produced in examples 1, 2, 3 and 4 of the present invention 3 XPS contrast plot of microspheres;
FIG. 6 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 The microspheres were used as electrocatalysts in 5mVs in 0.1M KOH saturated with nitrogen and 0.1M KOH saturated with argon, respectively -1 LSV plot measured at scan speed;
FIG. 7 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO obtained in example 4 of the present invention 3 The performance diagram of ammonia production and Faraday efficiency after testing under five groups of electric potentials when the microspheres are used as electrocatalysts;
FIG. 8 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO produced in examples 1, 2, 3 and 4 of the present invention 3 The performance comparison graph of ammonia yield and Faraday efficiency of the reaction of the microspheres as a catalyst;
FIG. 9 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO obtained in example 4 of the present invention 3 6-cycle performance test patterns performed at-0.3V (versus standard hydrogen electrode) with microspheres as electrocatalyst;
FIG. 10 is an oxygen-enriched product of example 4 of the present inventionVacancy bimetallic oxide OV-NiMnO 3 20 hour i-t stability test plot for microspheres as electrocatalyst.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings, but are not to be construed as limiting the scope of the invention.
Example 1
(1) 80mmol of urea was first dissolved in a mixed solution of 25mL of deionized water and 25mL of absolute ethanol 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 was added to the mixed solution and stirred for another 10min. Finally, the solution was transferred to a stainless steel autoclave of polytetrafluoroethylene (total capacity 50 mL) and maintained at 150 ℃ for 5h. After cooling to room temperature, the ni—mn precursor obtained by centrifugal separation was washed with deionized water and ethanol, and finally dried in a vacuum oven.
(2) The synthesized Ni-Mn precursor is transferred to a tube furnace and oxidized in an air atmosphere. Specifically, the Ni-Mn precursor is heated to 500 ℃ from room temperature and kept for 2 hours to obtain NiMnO 3 And (3) microspheres.
(3) 200mg NiMnO was added to the mixture 3 The microspheres were uniformly placed in a porcelain boat and transferred to a tube furnace where pyrolysis was performed in an argon atmosphere. Specifically, niMnO is formed 3 The microspheres are heated to 300 ℃ from room temperature and kept for 2 hours to obtain the bimetallic oxide OV-NiMnO which is rich in oxygen vacancies 3 And (3) microspheres.
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 an additional 20min. Finally, the solution is transferredInto a stainless steel autoclave of polytetrafluoroethylene (total capacity 60 mL) and maintained at 160℃for 7h. After cooling to room temperature, the ni—mn precursor obtained by centrifugal separation was washed with deionized water and ethanol, and finally dried in a vacuum oven.
(2) The synthesized Ni-Mn precursor is transferred to a tube furnace and oxidized in an air atmosphere. Specifically, the Ni-Mn precursor is heated to 550 ℃ from room temperature and kept for 2 hours to obtain NiMnO 3 And (3) microspheres.
(3) 200mg NiMnO was added to the mixture 3 The microspheres were uniformly placed in a porcelain boat and transferred to a tube furnace where pyrolysis was performed in an argon atmosphere. Specifically, niMnO is formed 3 The microspheres are heated to 350 ℃ from room temperature and kept for 2 hours to obtain the bimetallic oxide OV-NiMnO which is rich in oxygen vacancies 3 And (3) microspheres.
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 an additional 10min. Finally, the solution was transferred to a stainless steel autoclave of polytetrafluoroethylene (total capacity 70 mL) and maintained at 170 ℃ for 6h. After cooling to room temperature, the ni—mn precursor obtained by centrifugal separation was washed with deionized water and ethanol, and finally dried in a vacuum oven.
(2) The synthesized Ni-Mn precursor is transferred to a tube furnace and oxidized in an air atmosphere. Specifically, the Ni-Mn precursor is heated to 550 ℃ from room temperature and kept for 2 hours to obtain NiMnO 3 And (3) microspheres.
(3) NiMnO is added to 3 The microspheres were uniformly placed in a porcelain boat and transferred to a tube furnace where pyrolysis was performed in an argon atmosphere. Specifically, niMnO is formed 3 The microspheres are heated to 400 ℃ from room temperature and kept for 2 hours to obtain the bimetallic oxide OV-NiMnO which is rich in oxygen vacancies 3 And (3) microspheres.
Example 4
(1) First 120mmol was addedUrea was 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 an additional 20min. Finally, the solution was transferred to a stainless steel autoclave of polytetrafluoroethylene (total capacity 80 mL) and maintained at 180 ℃ for 7h. After cooling to room temperature, the ni—mn precursor obtained by centrifugal separation was washed with deionized water and ethanol, and finally dried in a vacuum oven.
(2) The synthesized Ni-Mn precursor is transferred to a tube furnace and oxidized in an air atmosphere. Specifically, the Ni-Mn precursor is heated to 600 ℃ from room temperature and kept for 2 hours to obtain NiMnO 3 And (3) microspheres.
(3) NiMnO is added to 3 The microspheres were uniformly placed in a porcelain boat and transferred to a tube furnace where pyrolysis was performed in an argon atmosphere. Specifically, niMnO is formed 3 The microspheres were heated from room temperature to 500 ℃ and held for 2h. Obtaining the bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 And (3) microspheres.
Test results:
FIG. 1 a shows an oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 Transmission electron microscope pictures of the microspheres; from the figure, OV-NiMnO was found 3 The whole microsphere has a spherical structure and is matched with NiMnO 3 The microspheres (shown in FIG. 1 b) showed no significant structural change compared to the microspheres, indicating that the introduction of oxygen vacancies was responsible for NiMnO 3 The structure of (3) is not affected.
FIG. 2 a shows an 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 was found 3 The microspheres have spherical structures with irregular surfaces, and are matched with NiMnO 3 The microspheres (shown as b in fig. 2) have no significant structural change compared to the microspheres.
FIG. 3 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 XRD patterns of the microspheres, 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 high and substantially coincides with the standard card.
FIG. 4 shows the oxygen vacancy-rich bimetallic oxides OV-NiMnO obtained in examples 1, 2, 3 and 4 of the present invention 3 ESR contrast plot of 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 had peaks at g=2.003, indicating that all four samples prepared by the examples had oxygen vacancies generated. And the peak intensity increases with increasing pyrolysis temperature, indicating that increasing pyrolysis temperature can increase the number of oxygen vacancies.
FIG. 5 shows the oxygen vacancy-rich bimetallic oxides OV-NiMnO produced in examples 1, 2, 3 and 4 of the present invention 3 XPS contrast plot of microspheres; from the figure, it can be seen that OV-NiMnO prepared in example 1, example 2, example 3 and example 4 3 The oxygen element characteristic peak of the microsphere, wherein the peak at 531.7eV represents the oxygen vacancy peak, and the OV-NiMnO is obtained after calculation by fitting the peak area 3 Concentration values of oxygen vacancies of microspheres, OV-NiMnO in example 1 3 The concentration of oxygen vacancies in the microspheres was 21.5%, OV-NiMnO in example 2 3 The concentration of oxygen vacancies in the microspheres was 23.6%, OV-NiMnO in example 3 3 The concentration of oxygen vacancies in the microspheres was 25.4% and OV-NiMnO in example 4 3 The concentration value of the oxygen vacancies of the microspheres is 32.2%. Illustrating the OV-NiMnO produced at different pyrolysis temperatures 3 The concentration of oxygen vacancies varies and increases with increasing pyrolysis temperature.
FIG. 6 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 of the present invention 3 Microspheres as catalysts at 5mVs in nitrogen-saturated and argon-saturated electrolytes, respectively -1 From the graph, it can be seen 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 occurred in the nitrogen saturated electrolyte,indicating that the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 3 The microspheres have electrocatalytic nitrogen reduction properties.
FIG. 7 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO obtained 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 production at five sets of voltages with microspheres used as catalysts. As can be seen from the graph, the maximum ammonia production was 34.15. Mu.g/h/mg at a voltage of-0.3V (relative to a standard hydrogen electrode) cat . The right graph shows the faraday efficiencies obtained at five sets of voltages, and it is seen from the graph that the maximum faraday efficiency is 14.5% at a voltage of-0.1V (versus standard hydrogen electrode).
FIG. 8 shows the oxygen vacancy-rich bimetallic oxides OV-NiMnO produced in examples 1, 2, 3 and 4 of the present invention 3 Performance of microspheres as catalyst versus faraday efficiency; it can be seen from the figure that the pyrolysis temperature of the different embodiments is different, and as the pyrolysis temperature is increased, the concentration of oxygen vacancies is gradually increased, and the catalytic ammonia production performance is also gradually increased.
FIG. 9 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO obtained in example 4 of the present invention 3 6 cycle performance test plots at-0.3V (vs. standard hydrogen electrode) with microspheres as electrocatalyst. From the figure, it can be seen that the oxygen vacancy-rich bimetallic oxide OV-NiMnO prepared in example 4 was obtained during six repetitions of the test 3 The ammonia yield and Faraday efficiency of the electrocatalyst with microspheres only slightly fluctuated, and the performance of the electrocatalyst has no obvious performance decline, which indicates that the bimetallic oxide OV-NiMnO rich in oxygen vacancies prepared in example 4 3 The performance repeatability of the microspheres is excellent.
FIG. 10 shows the oxygen vacancy-rich bimetallic oxide OV-NiMnO obtained in example 4 of the present invention 3 20 hour i-t stability test plot for microspheres as electrocatalyst. As can be seen from the graph, the i-t curve is smoothed in the stability test for 20 hours, illustrating the oxygen vacancy-rich bimetal oxygen prepared in example 4Compounds OV-NiMnO 3 The reaction of the microspheres as electrocatalyst has excellent stability.
In conclusion, the bimetallic oxide OV-NiMnO rich in oxygen vacancies provided by the invention 3 The preparation method of the microspheres has simple synthesis process, mild reaction conditions and oxygen vacancy-enriched bimetallic oxide OV-NiMnO 3 The reaction of the microspheres as the catalyst has high ammonia yield and excellent performance of Gao Fala first efficiency, and can be used for preparing ammonia by electrocatalytic nitrogen reduction, so that the electrochemical performance of preparing ammonia by electrocatalytic nitrogen reduction is obviously improved.
Finally, it should be noted that: the embodiments described above are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. Oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 The preparation method of the microspheres is characterized by comprising 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 performing hydrothermal reaction to obtain a Ni-Mn precursor;
s2, placing the Ni-Mn precursor into a tube furnace and oxidizing under the air environment condition, and naturally cooling the tube furnace to room temperature to obtain NiMnO 3 A microsphere;
s3, mixing the NiMnO 3 Placing the microspheres in a tubular furnace and pyrolyzing under the condition of argon saturation, and naturally cooling the tubular furnace to room temperature to obtain the bimetallic oxide OV-NiMnO rich in oxygen vacancies 3 And (3) microspheres.
2. The oxygen vacancy-enriched bis of claim 1Metal oxide OV-NiMnO 3 The preparation method of the microspheres is characterized in that in the step S1, the molar ratio of the nickel source compound to the manganese source compound to the organic compound is 1:1:10, and the molar amount of the nickel source compound is 0.008-0.012 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 microspheres is characterized in that the stirring temperature in the step S1 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 the oxidation temperature in the step S2 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 by comprising the following steps ofS3, pyrolysis temperature is 300-500 ℃ and pyrolysis time is 2h.
9. Oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 Microspheres, characterized in that according to any one of the claims 1-8 the oxygen vacancy enriched bi-metal oxide OV-NiMnO 3 The preparation method of the microspheres.
10. The oxygen vacancy-rich bimetallic oxide OV-NiMnO of claim 9 3 Microspheres, characterized in that the oxygen vacancy-rich bimetallic oxide OV-NiMnO 3 The concentration value of oxygen vacancies in the microspheres is 21.5% -32.2%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019053749A1 (en) * | 2017-09-08 | 2019-03-21 | Haskoli Islands | Electrolytic ammonia production using transition metal oxide catalysts |
| CN110227474A (en) * | 2019-07-04 | 2019-09-13 | 中国科学技术大学 | A kind of LaCoO with Lacking oxygen3The preparation method and application of nano material |
| CN111686714A (en) * | 2020-07-27 | 2020-09-22 | 兰州交通大学 | Preparation method of oxygen-enriched vacancy cerium-molybdenum-based nanosphere electrochemical nitrogen fixation catalyst |
| CN112501650A (en) * | 2020-11-06 | 2021-03-16 | 北京大学深圳研究生院 | Multi-vacancy transition metal layered dihydroxy compound, preparation method and application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019053749A1 (en) * | 2017-09-08 | 2019-03-21 | Haskoli Islands | Electrolytic ammonia production using transition metal oxide catalysts |
| CN111094629A (en) * | 2017-09-08 | 2020-05-01 | 冰岛大学 | Electrolytic production of ammonia using transition metal oxide catalysts |
| CN110227474A (en) * | 2019-07-04 | 2019-09-13 | 中国科学技术大学 | A kind of LaCoO with Lacking oxygen3The preparation method and application of nano material |
| CN111686714A (en) * | 2020-07-27 | 2020-09-22 | 兰州交通大学 | Preparation method of oxygen-enriched vacancy cerium-molybdenum-based nanosphere electrochemical nitrogen fixation catalyst |
| CN112501650A (en) * | 2020-11-06 | 2021-03-16 | 北京大学深圳研究生院 | Multi-vacancy transition metal layered dihydroxy compound, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 利用不同氢源及氮源电化学合成氨研究进展与挑战;关浩然;化工进展;第41卷(第8期);4098-4111 * |
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