CN113912114A - Electrocatalytic material VS for ENRR2Preparation method of (1) - Google Patents
Electrocatalytic material VS for ENRR2Preparation method of (1) Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 9
- NGTSQWJVGHUNSS-UHFFFAOYSA-N bis(sulfanylidene)vanadium Chemical compound S=[V]=S NGTSQWJVGHUNSS-UHFFFAOYSA-N 0.000 claims abstract description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 31
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 2
- 238000001914 filtration Methods 0.000 abstract description 4
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 abstract 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 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 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- FHANEPRSLAMSJU-UHFFFAOYSA-N vanadium(4+);disulfide Chemical compound [S-2].[S-2].[V+4] FHANEPRSLAMSJU-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
-
- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/32—Spheres
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
A preparation method of an electrocatalytic material VS2 for ENRR belongs to the field of electrocatalytic nitrogen fixation, and comprises the steps of mechanically mixing precursors, performing microwave hydrothermal treatment on the precursor solution, filtering, washing and vacuum drying the solid obtained by the hydrothermal treatment to obtain VS2. The invention is mainly used for preparing VS2An electrocatalytic nitrogen fixation material solves VS of common hydrothermal preparation2The method is used for solving the problem of poor ENRR performance. In addition, vanadium disulfide VS is hydrothermally obtained by taking sodium orthovanadate as a vanadium source and taking thioacetamide as a sulfur source2‑xCompared with the prior art, the method takes ammonium metavanadate as a vanadium source to obtain the vanadium-vanadium mixed vanadium oxide with thioacetamide by hydrothermal methodPure + 4V vanadium disulfide VS2And the corresponding ENRR performance is more excellent.
Description
Technical Field
The invention belongs to the field of ammonia production by electrocatalytic reduction of nitrogen, and particularly discloses an electrocatalytic material VS for ENRR2The preparation method of (1).
Background
With the continuous consumption of non-renewable fossil fuels and the increasing prominence of energy crisis and environmental deterioration caused by excessive emission of greenhouse gases, a novel clean energy with abundant reserves is searched to gradually replace the fossil fuels, and the realization of green sustainable development is imperative. The ammonia gas is used as a clean energy carrier, the energy density of the ammonia gas is higher than that of hydrogen gas, combustion products are also environment-friendly, and the ammonia gas is used as N of ammonia source in the atmosphere2Is quite abundant. NH in contrast to compressed hydrogen (storage and transport)3Easy liquefaction at ambient temperature and a pressure of ≈ 8bar, providing a high volumetric energy density (10.5mJ/L) which is more than twice that of compressed hydrogen at 700bar (5mJ/L), much lower than liquid H2The cost of storage and transportation. In addition, ammonia is an important precursor for ammonium fertilizers, certain drugs, explosives, and amino acids. However, the Haber-Bosch process which is high in energy consumption and greenhouse gas emission is mainly adopted in the industrial ammonia production at present. In order to keep clean energy clean, materials capable of performing ammonia synthesis at normal temperature and normal pressure, such as bionic nitrogen fixation enzyme, nitrogen fixation photocatalyst, nitrogen fixation electrocatalyst and the like, are increasingly concerned by people.
The electrocatalytic nitrogen fixation is realized, and the preparation of the electrocatalysts with excellent performance is a key step, and the following characteristics are often needed: good mass transfer capacity and conductivity, certain mechanical strength and low energy consumption in the synthesis process. In the traditional catalyst preparation process, a common hydrothermal method which is often used is long in reaction time, corresponding energy consumption is low, and physical characteristics of the obtained material are difficult to unify. Furthermore, sodium orthovanadate Na has been widely used heretofore3VO4As a V source to hydrothermally react with thioacetamide to obtain vanadium disulfide VS2-xThe preparation methods are different, and the vanadium disulfide VS is obtained by taking ammonium metavanadate as a precursor2The valence states are purer and are all +4 valence. The ENRR performance is also more excellent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for conveniently and rapidly preparing VS for electrocatalytic nitrogen fixation2The method of the base material can reduce the consumption of the synthesis of the material at the early stage while having good catalytic performanceEnergy and time.
In order to solve the technical problem, the invention provides vanadium disulfide VS for electrocatalytic reduction of nitrogen2The preparation method comprises the steps of mechanically mixing precursors, performing microwave hydrothermal treatment on the precursor solution, filtering, washing and vacuum drying the solid obtained by the hydrothermal treatment to obtain VS2. The precursor solution is prepared from ammonium metavanadate NH4VO3Thioacetamide and ultrapure water.
Further, the molar ratio of the ammonium metavanadate to the thioacetamide is 1: 5; the amount of pure water used is preferably 30 to 50mL, preferably 40mL, per 3mmol of ammonium metavanadate.
Further, the mechanical mixing is realized by magnetic stirring, and the specific stirring time is 1 h.
Further, the specific process of the microwave hydrothermal method comprises the following steps: heating to 120 deg.C from room temperature for 10min, and maintaining the temperature for 8 min; then heating to 150 ℃ after 10min, and preserving heat for 8min at the temperature; then heating to 180 ℃ after 10min, and keeping the temperature for 120 min; finally, naturally cooling to room temperature;
furthermore, solvents used for filtering, filtering and washing the solid obtained by the hydrothermal method are ultrapure water and absolute ethyl alcohol respectively, and the washing times are 3 times.
Further, the vacuum drying conditions are as follows: 30MPa, 60 ℃ and 12 h.
The invention ensures that the prepared material has certain catalytic activity, shortens the time required by material synthesis, reduces the energy consumption in the preparation process, and ensures that the obtained material has uniform micro-morphology and concentrated size distribution. The above features contribute to the intensive study of the ENRR process.
Drawings
FIG. 1 shows an electrocatalytic material VS for ENRR in accordance with the present invention2Schematic of the micro-topography of (a);
FIG. 2 is an electrocatalytic material VS for ENRR in accordance with the present invention2And VS2-xX-ray photoelectron spectroscopy of (a);
FIG. 3 is an electrocatalytic material VS for ENRR in accordance with the present invention2Linear sweep voltammetryAn intent;
FIG. 4 shows an electrocatalytic material VS for ENRR in accordance with the present invention2A chronoamperometric schematic of (a);
FIG. 5 is an electrocatalytic material VS for ENRR in accordance with the present invention2And VS2-xComparison of ammonia yields to schematic;
FIG. 6 is an electrocatalytic material VS for ENRR in accordance with the present invention2And VS2-xSchematic representation of faradaic efficiency versus ammonia yield of (a);
FIG. 7 is a schematic diagram of the cell configuration for the ENRR of the present invention.
Detailed Description
The present invention will be described in more detail with reference to the following embodiments, but the present invention is not limited to the following examples.
An electrocatalytic material VS for ENRR shown in combination with FIG. 12The material mainly comprises microspheres with the particle size of about 1 mu m.
The preparation method comprises the following steps: 3mmol of ammonium metavanadate, 15mmol of thioacetamide and 40mL of ultrapure water are mixed, and the mixture is magnetically stirred for 1 hour to obtain a light green turbid liquid. Transferring the liquid into a microwave reaction kettle, and carrying out hydrothermal synthesis according to the following processes: heating to 120 deg.C from room temperature for 10min, and maintaining the temperature for 8 min; then heating to 150 ℃ for 10min, and preserving the heat for 8min at the temperature; then heating to 180 ℃ for 10min, and keeping the temperature for 120 min; and finally, naturally cooling to room temperature. The power adopted by the microwave reaction kettle is 1000W.
And cooling to room temperature, carrying out vacuum filtration on the obtained black liquid, washing with ultrapure water and absolute ethyl alcohol for 3 times respectively, and finally carrying out vacuum drying for 12 hours to obtain a black solid.
Preparing an electrode: weighing 5mg of vanadium disulfide VS2Dispersing in a liquid mixed with 20 μ L of membrane solution, 326 μ L of ultrapure water and 654 μ L of anhydrous ethanol, performing ultrasonic treatment for 1 hr to obtain an ink-like liquid, and uniformly coating 20 μ L of the liquid on 1 × 2cm carbon paper with a coating area of 1cm2。
In the embodiment, the electrode is subjected to micro-morphology characterization and analysis by using a scanning electron microscope and a transmission electron microscope, and as can be seen in fig. 1, the material mainly consists of 1 μm micro-spheres.
FIG. 2 shows a material VS according to the invention2X-ray photoelectron spectroscopy of (a); it can be seen from figure 2 that only +4 valences are present in the vanadium disulphide obtained according to the above method, whereas both +2 and +4 valences are present in the material obtained with sodium orthovanadate as the vanadium source.
FIG. 3 is a schematic diagram of linear sweep voltammetry for a material of the invention; the specific experimental parameters are as follows: the initial potential is 0V; the termination potential is-1.4V; the scanning speed is 0.05V/s; the dot interval is 0.001V; the sensitivity is 0.1A/V; the different atmospheres were achieved by continuously aerating the cell shown in FIG. 7 at a gas flow rate of 30mL/min for 30 min. It can be seen from fig. 3 that the current of the material is significantly larger than that of the material in the argon atmosphere in the nitrogen atmosphere, and the material is preliminarily proved to have certain electrocatalytic nitrogen fixation performance.
FIG. 4 is a chronoamperometric schematic of the material of the present invention; the specific parameters are as follows: potential settings are-0.2, -0.25, -0.30, -0.35, -0.40V vs. RHE, respectively; the dot interval is 0.05 s; the running time is 7200 s; the sensitivity was 0.1A/V. As can be seen from fig. 4, the corresponding current fluctuates within a small range at different potentials, demonstrating a certain catalytic stability of the material.
FIG. 5 is a schematic illustration of ammonia production of the material of the present invention; as can be seen from FIG. 5, the ammonia yield of the material of the invention reaches up to 41.21 mu g h at a potential of-0.3V vs. RHE-1mgcat -1And VS is2-xNot only was the optimum reduction potential more negative (-0.7V vs. RHE) but the highest ammonia yield was only 17.57. mu. g h-1mgcat -1. The material of the invention is proved to have more excellent electro-catalysis ammonia production performance. The ammonia production amount calculation formula is as follows:
FIG. 6 is a schematic representation of the Faraday efficiency of the material of the present invention; as can be seen from FIG. 6, at a potential of-0.3V vs. RHE, the FE value of the material of the present invention reaches up to 35.5%, while VS is higher than that of the material of the present invention2-xThe highest FE value of (a) is only 1.06%. The material of the invention is proved to have higher selectivity. The FE calculation formula is as follows:
FE is Faraday efficiency, unit is%; f is the Faraday constant and has a value of 96500C mol-1(ii) a Q is the total charge consumption of the electrolysis process and is given in C.
FIG. 7 is a schematic diagram of the cell structure of the material of the present invention.
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent.
Claims (7)
1. Vanadium disulfide VS for electrocatalytic reduction of nitrogen2The preparation method of the material is characterized by comprising the steps of mechanically mixing precursors, performing microwave hydrothermal treatment on the precursor solution, performing suction filtration, washing and vacuum drying on the solid obtained by the hydrothermal treatment to obtain VS2(ii) a The precursor solution is prepared from ammonium metavanadate NH4VO3Thioacetamide and ultrapure water;
the molar ratio of the ammonium metavanadate to the thioacetamide is 1: 5.
2. The specific process of the microwave hydrothermal method comprises the following steps: heating to 120 deg.C from room temperature for 10min, and maintaining the temperature for 8 min; then heating to 150 ℃ after 10min, and preserving heat for 8min at the temperature; then heating to 180 ℃ after 10min, and keeping the temperature for 120 min; and finally, naturally cooling to room temperature.
3. The method according to claim 1, wherein the amount of pure water is preferably 30 to 50mL, preferably 40mL, per 3mmol of ammonium metavanadate.
4. The method according to claim 1, wherein the solvents used for the hydrothermal suction filtration and washing of the solid are ultrapure water and absolute ethyl alcohol, and the number of washing times is 3.
5. The method according to claim 1, wherein the vacuum drying is carried out under the following conditions: 30MPa, 60 ℃ and 12 h.
6. Vanadium disulfide VS prepared by the process according to any one of claims 1 to 52。
7. Vanadium disulfide VS prepared by the process according to any one of claims 1 to 52The method is used for preparing ammonia by electrocatalytic reduction of nitrogen.
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Cited By (1)
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| CN113862717A (en) * | 2021-10-12 | 2021-12-31 | 济南大学 | Rose type catalyst VS2@Bi2O3Preparation method of/CC and application thereof in nitrogen reduction |
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| CN104383954A (en) * | 2014-11-27 | 2015-03-04 | 陕西科技大学 | Nanometer clavate nonmetallic doped BiPO4 photocatalyst and preparation method as well as application of nanometer clavate nonmetallic doped BiPO4 photocatalyst |
| CN109019686A (en) * | 2018-10-01 | 2018-12-18 | 湘潭大学 | A kind of preparation method and application of airsetting glue vanadium disulfide nano material |
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