CN111514879B - Synthesis method and application of indium-based vanadium oxide catalyst - Google Patents
Synthesis method and application of indium-based vanadium oxide catalyst Download PDFInfo
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 42
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 42
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 39
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 34
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 11
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 11
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 10
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
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- 230000002194 synthesizing effect Effects 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 229910021607 Silver chloride Inorganic materials 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- -1 noble metals Chemical class 0.000 description 2
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
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- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- 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
Abstract
A synthetic method of an indium-based vanadium oxide catalyst and an application thereof belong to the technical field of electrocatalysis. In order to solve the problems of high material cost, complex synthesis process, easy inactivation of catalyst and the like of the existing electro-catalysis synthesis ammonia, the method comprises the following steps: adding indium nitrate into a three-necked bottle filled with a mixed solvent of oleic acid, oleylamine and octadecene, degassing in an inert atmosphere, and stirring at the temperature of 140-190 ℃ for reaction; dissolving sodium metavanadate in a mixed solution of nitric acid and water, stirring and dissolving, dripping the solution into a three-necked bottle, carrying out condensation reflux reaction at the temperature of 140-190 ℃ for 30-40min under the protection of inert atmosphere, and naturally cooling to room temperature; adding mixed solution of n-hexane and anhydrous ethanol, washing, layering, washing the upper layer with mixed solution of n-hexane and anhydrous ethanol, centrifuging, and vacuum drying. The synthesis method has the advantages of simple operation, simple equipment, short reaction time and good repeatability, and the two morphologies of the electrocatalysts have good electrocatalysis ammonia synthesis performance and very good stability.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a synthesis method and application of an indium-based vanadium oxide catalyst.
Background
Ammonia is an important inorganic chemical product, and the synthetic ammonia industry has important significance for human production and life. Currently, nitrogen and H are fixed industrially by the Haber-Bosch process2The reaction takes place to synthesize ammonia. This process needs to be carried out under severe high temperature and pressure conditions. Due to H2From the reforming of natural gas, thus requiring a huge energy consumption and producing a large amount of the greenhouse gas CO2Causing serious environmental pollution and aggravating global warming.
The electro-catalysis synthesis of ammonia can be carried out at normal temperature and normal pressure due to mild reaction conditions, and is expected to replace the traditional Haber-Bosch method of reaction at high temperature and high pressure. At present, the materials for synthesizing ammonia by electrocatalysis are mainly compounds such as noble metals, iron-based compounds, molybdenum-based compounds, bismuth-based compounds and the like, but still have a plurality of defects in the catalytic reaction process. For example, the practical application of the catalyst is restricted by the defects of high cost, complex synthesis process, easy inactivation of the catalyst and the like. Meanwhile, the morphology of the material has great influence on the activity of the electro-catalytic synthesis of ammonia. It is therefore a focus of research to find a new electrocatalyst to solve the above problems. The indium-based compound has the characteristics of good conductivity, stable chemical property and the like. However, currently, indium-based materials are rarely reported for methods for electrocatalytic synthesis of ammonia. Therefore, the synthesis of the stable indium-based catalyst for the electro-catalytic synthesis of ammonia has important significance.
Disclosure of Invention
The invention aims to solve the problems of high material cost, complex synthesis process, easy inactivation of the catalyst and the like of the existing electro-catalysis ammonia synthesis, and provides a synthesis method of an indium-based vanadium oxide catalyst and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for synthesizing an indium-based vanadium oxide catalyst, comprising the steps of:
the method comprises the following steps: adding indium nitrate into a three-necked bottle filled with a mixed solvent of oleylamine, oleic acid and octadecene, degassing in an inert atmosphere, and stirring at the temperature of 140-190 ℃ for reaction;
step two: dissolving sodium metavanadate in a mixed solution of nitric acid and water, stirring and dissolving, dropwise adding the solution into the three-necked bottle in the step one, carrying out condensation reflux reaction at 140-190 ℃ for 30-40min under the protection of inert atmosphere, and naturally cooling to room temperature;
step three: adding mixed solution of n-hexane and anhydrous ethanol for washing, layering the solution from top to bottom, washing the upper layer with mixed solution of n-hexane and anhydrous ethanol, centrifuging, and vacuum drying.
Compared with the prior art, the invention has the beneficial effects that: the method takes indium nitrate as a raw material, takes octadecene, oleic acid and oleylamine as solvents, and carries out nucleation and crystal growth with a device of condensation reflux of another phase of sodium metavanadate solution under the protection of inert atmosphere. And controlling different shapes of the indium-based vanadium oxide by controlling different temperatures in condensation reflux. The synthesis method has the advantages of simple operation, simple equipment, short reaction time and good repeatability, and the synthetic material is used as an electrocatalyst to be applied to the electrocatalytic synthesis of ammonia. The two morphologies of the electrocatalyst have good performance of electrocatalytic ammonia synthesis and good stability.
Drawings
FIG. 1 is a schematic diagram of a process for preparing indium-based vanadium oxide;
FIG. 2 is a scanning electron microscope topography of the indium-based vanadium oxide prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope topography of the indium-based vanadium oxide prepared in example 2 of the present invention;
FIG. 4 is a schematic diagram of the morphology of the indium-based vanadium oxide catalyst obtained at a reaction temperature of 160 ℃ according to the present invention.
Detailed description of the preferred embodiments
The technical solution of the present invention is further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention.
The first embodiment is as follows: the present embodiment describes a method for synthesizing an indium-based vanadium oxide catalyst, which comprises the following steps:
the method comprises the following steps: adding indium nitrate into a three-necked bottle filled with a mixed solvent of oleic acid, oleylamine and octadecene, degassing in an inert atmosphere, and stirring at the temperature of 140-190 ℃ for reaction;
step two: dissolving sodium metavanadate in a mixed solution of nitric acid and water, stirring and dissolving, dropwise adding the solution into the three-necked bottle in the step one, carrying out condensation reflux reaction at 140-190 ℃ for 30-40min under the protection of inert atmosphere, and naturally cooling to room temperature;
step three: adding mixed solution of n-hexane and anhydrous ethanol, washing, layering the solution from top to bottom, washing the upper layer with mixed solution of n-hexane and anhydrous ethanol for 3-5 times, centrifuging, and vacuum drying.
In the heating process, octadecene is used as a solvent, oleylamine is used as a reducing agent, oleic acid is used as a stabilizing agent, and indium ions are connected with carboxylic acid in the oleic acid; then adding sodium metavanadate, wherein the metavanadate radical ions are negatively charged to attract indium ions, finally forming crystal nuclei of the indium-based vanadium oxide, and then growing crystals with different shapes under the regulation and control of different temperatures.
The second embodiment is as follows: in the method for synthesizing an indium-based vanadium oxide catalyst according to the first embodiment, in the first step, the volume ratio of oleic acid, oleylamine, and octadecene is 1: 1: 10.
the third concrete implementation mode: in the second step of the method for synthesizing an indium-based vanadium oxide catalyst, the volume ratio of nitric acid to water is 1: 5.
the fourth concrete implementation mode: in a method for synthesizing an indium-based vanadium oxide catalyst according to a first embodiment, a molar ratio of indium nitrate to sodium metavanadate is 1: 2.
the fifth concrete implementation mode: in the first and second steps of the method for synthesizing an indium-based vanadium oxide catalyst, the reaction temperature is 140-.
The sixth specific implementation mode: in the method for synthesizing an indium-based vanadium oxide catalyst according to the first embodiment, in the first step and the second step, the reaction temperature is 170-.
140-160 takes a rod shape as a main part, the temperature rise is gradually converted from the rod shape to a sheet shape, 170-190 ℃ takes a sheet shape as a main part, 190 ℃ is completely converted into a sheet shape, when the temperature is between 160-170 ℃, the morphology of the catalyst is sheet shape and rod shape, as shown in figure 4, the electron microscope morphology of the indium-based vanadium oxide catalyst obtained under the reaction condition of 160 ℃, can show the conversion from the rod shape to the sheet shape.
The seventh concrete implementation mode: the method for synthesizing an indium-based vanadium oxide catalyst according to the first embodiment comprises the first step and the second step, wherein the rotation speed of stirringIs 100r/min-300 r/min; the inert atmosphere is N2Or Ar.
The specific implementation mode is eight: in the third step, the centrifugal rotating speed is 6000r/min, and the time is 5-10 min; the temperature of the vacuum drying is 60 ℃, and the time is 6-8 h.
The specific implementation method nine: in the third step, the volume ratio of the n-hexane to the absolute ethyl alcohol is 1: 3.
the detailed implementation mode is ten: an application of the indium-based vanadium oxide catalyst prepared in any one of the first to ninth embodiments in the electrocatalytic synthesis of ammonia, which is used as an electrocatalytic material in the preparation of ammonia gas through electrocatalytic nitrogen reduction, comprises the following specific steps: indium-based vanadium oxide materials with different shapes are coated on carbon paper to form a working electrode, Ag/AgCl is used as a reference electrode, a Pt sheet is used as a counter electrode, HCl is used as electrolyte, a three-electrode reaction device is adopted, and under the assistance of an electric field, specific voltage is applied to carry out nitrogen reduction and synthesis of ammonia.
Example 1:
a method for synthesizing an indium-based vanadium oxide catalyst, comprising the steps of:
0.5mmol of indium nitrate was added to a three-necked flask containing a mixed solvent of 1ml of oleic acid, 1ml of oleylamine and 10ml of octadecene in N2Degassing, and stirring at 190 deg.C for 100 r/min. Simultaneously dissolving 1mmol sodium metavanadate in a mixed solution of 2ml nitric acid and 10ml water, stirring for dissolving at 100r/min, and then dropwise adding the solution into the three-necked flask solution, and adding N2Under the protection of 190 ℃ and under the control of reaction temperature, carrying out condensation reflux reaction for 30 min. After the reaction is finished, the heat source is removed and the reaction product is cooled to room temperature. Adding a mixed solution (volume ratio is 1: 3) of n-hexane and absolute ethyl alcohol for washing, layering the solution up and down, and discarding the bottom solution. Washing the upper layer precipitate with mixed solution of n-hexane and anhydrous ethanol for 3 times, centrifuging at 6000 rpm for 5min, and oven drying in vacuum drying oven at 60 deg.C for 6 hr to obtain flaky indium-based vanadium oxide, as shown in FIG. 2.
Example 2:
a method for synthesizing an indium-based vanadium oxide catalyst, comprising the following steps:
0.5mmol of indium nitrate was added to a three-necked flask containing a mixed solvent of 1ml of oleic acid, 1ml of oleylamine and 10ml of octadecene in N2Degassing, and stirring at 230r/min at 150 ℃. Simultaneously dissolving 1mmol sodium metavanadate in a mixed solution of 2ml nitric acid and 10ml water, stirring at 230r/min for dissolving, dropwise adding the solution into the three-necked flask solution, and adding N2Under the protection of 150 ℃, the reaction is carried out for 30min by condensation reflux. After the reaction is finished, the heat source is removed and the reaction product is cooled to room temperature. Adding a mixed solution (volume ratio is 1: 3) of n-hexane and absolute ethyl alcohol for washing, layering the solution up and down, and discarding the bottom solution. Washing the upper layer precipitate with mixed solution of n-hexane and anhydrous ethanol for several times, centrifuging at 6000 rpm for 5min, and oven drying in vacuum drying oven at 60 deg.C for 7 hr to obtain rod-shaped indium-based vanadium oxide, as shown in FIG. 3.
Example 3:
preparation of working electrode
(1) Cutting 1 × 2cm carbon paper, dissolving in 50ml ethanol solution (volume ratio of ethanol to water is 1:1), ultrasonic treating for 30min, taking out, and air drying at room temperature.
(2) 10mg of the catalytic material prepared in example 1 was weighed and put into a 2.5ml centrifuge tube, 40. mu.l of Nafion solution + 960. mu.l of an alcohol-water mixture (volume ratio of ethanol to water 1:1) was added, and the mixture was ultrasonically dispersed in an ultrasonic cleaner for 1 hour.
(3) And (3) transferring 40 mu l of the dispersed suspension from the step (2) by using a liquid transfer gun, uniformly dripping the suspension on the carbon paper of the step (1), wherein the dripping area is 1 x 1cm, and airing at room temperature to prepare the working electrode of the flaky indium-based vanadium oxide catalyst.
(4) 10mg of the catalytic material prepared in example 2 was weighed and placed in a 2.5ml centrifuge tube, 40. mu.l of Nafion solution + 960. mu.l of an alcohol-water mixture (volume ratio of ethanol to water is 1:1) was added, and ultrasonic dispersion was performed for 1 hour.
(5) And (3) transferring 40 mu l of the dispersed suspension from the step (4) by using a liquid transfer gun, uniformly dripping the suspension on the carbon paper of the step (1), wherein the dripping area is 1 x 1cm, and airing at room temperature to prepare the working electrode of the rod-shaped indium-based vanadium oxide catalyst.
Example 4:
electrocatalytic ammonia synthesis performance test
Adopting a three-electrode reaction device, adding 211 proton exchange membrane between a cathode reactor and a reactor, respectively putting (3) or (5) in the cathode reactor as a working electrode, an Ag/AgCl reference electrode, putting a Pt sheet in an anode reactor as a counter electrode, respectively adding 50ml of 0.1mol/L HCl electrolyte in each of the two reactors, and continuously introducing N under sealing2After 30min, the gas solubility reached saturation. Under the assistance of an electric field, the reaction is respectively tested for 2h under-0.3V potential, the electrolyte in the cathode is removed, and the electrocatalytic ammonia synthesis performance of the two morphological materials (3) and (5) is evaluated at 655nm by an indophenol blue color development method. The yield of the ammonia synthesized by the catalyst with the rod-shaped morphology is 6.5-7.1 mu gh-1mg-1The productivity of the catalyst with sheet shape for synthesizing ammonia is 23-25.1 mu gh-1mg-1The productivity of the flake morphology is superior to the rod morphology. The two catalysts in the shapes can keep stable yield after multiple cycles, and the indium-based vanadium oxide electrocatalytic material has good performance of synthesizing ammonia by electrocatalytic nitrogen reduction.
Claims (10)
1. A method for synthesizing an indium-based vanadium oxide catalyst is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: adding indium nitrate into a three-necked bottle filled with a mixed solvent of oleic acid, oleylamine and octadecene, degassing in an inert atmosphere, and stirring at the temperature of 140-190 ℃ for reaction;
step two: dissolving sodium metavanadate in a mixed solution of nitric acid and water, stirring and dissolving, dropwise adding the solution into the three-necked bottle in the step one, carrying out condensation reflux reaction at 140-190 ℃ for 30-40min under the protection of inert atmosphere, and naturally cooling to room temperature;
step three: adding mixed solution of n-hexane and anhydrous ethanol for washing, layering the solution from top to bottom, washing the upper layer with mixed solution of n-hexane and anhydrous ethanol, centrifuging, and vacuum drying.
2. The method of synthesizing an indium-based vanadium oxide catalyst according to claim 1, wherein: in the first step, the volume ratio of the oleic acid to the oleylamine to the octadecene is 1: 1: 10.
3. the method of synthesizing an indium-based vanadium oxide catalyst according to claim 1, wherein: in the second step, the volume ratio of the nitric acid to the water is 1: 5.
4. the method of synthesizing an indium-based vanadium oxide catalyst according to claim 1, wherein: the mol ratio of the indium nitrate to the sodium metavanadate is 1: 2.
5. the method of synthesizing an indium-based vanadium oxide catalyst according to claim 1, wherein: in the first step and the second step, the reaction temperature is 140-160 ℃.
6. The method of synthesizing an indium-based vanadium oxide catalyst according to claim 1, wherein: in the first step and the second step, the reaction temperature is 170-190 ℃.
7. The method of synthesizing an indium-based vanadium oxide catalyst according to claim 1, wherein: in the first step and the second step, the rotating speed of the stirring is 100r/min-300 r/min; the inert atmosphere is N2Or Ar.
8. The method of synthesizing an indium-based vanadium oxide catalyst according to claim 1, wherein: in the third step, the rotating speed of the centrifugation is 6000r/min, and the time is 5-10 min; the temperature of the vacuum drying is 60 ℃, and the time is 6-8 h.
9. The method of synthesizing an indium-based vanadium oxide catalyst according to claim 1, wherein: in the third step, the volume ratio of the n-hexane to the absolute ethyl alcohol is 1: 3.
10. use of an indium-based vanadium oxide catalyst prepared according to any one of claims 1 to 9 in the electrocatalytic synthesis of ammonia, characterized in that: the material is used as an electrocatalytic material to be applied to the preparation of ammonia gas through electrocatalytic nitrogen reduction.
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