CN111701598A - Efficient iron-molybdenum-based nitrogen reduction electrocatalyst and preparation method thereof - Google Patents
Efficient iron-molybdenum-based nitrogen reduction electrocatalyst and preparation method thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 27
- 230000009467 reduction Effects 0.000 title claims abstract description 21
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 title claims abstract 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 239000002073 nanorod Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 239000011858 nanopowder Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000000137 annealing Methods 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 238000011056 performance test Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017116 Fe—Mo Inorganic materials 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009620 Haber process Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 8
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/50—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
Abstract
In the aspect of nitrogen reduction, the haber process has high consumption, high pollution and low conversion rate, so that the development of the preparation with simple operation, low consumption, low pollution and high conversion rate is concerned. The invention develops an efficient iron-molybdenum-based nitrogen reduction electrocatalyst and a preparation method thereof. Firstly, dissolving iron source in distilled water under stirring, transferring into polytetrafluoroethylene lining stainless steelAnd (3) in a steel autoclave, cooling to room temperature after hydrothermal treatment, centrifuging, collecting precipitate, and drying. And carrying out hydrothermal treatment on the obtained iron-containing precursor nano powder, a molybdenum source and sulfur source mixed suspension, centrifugally collecting obtained iron-containing, molybdenum and sulfur precipitates, and further washing the precipitates for several times by using distilled water and ethanol. Finally, the dried precipitate containing iron, molybdenum and sulfur is thermally annealed in a tube furnace to obtain FeMo3S4And (4) nanorods. Nanorod-shaped FeMo3S4Is an efficient and stable NRR electrocatalyst. NH at-0.3V (vs. standard hydrogen electrode)3The yield was 65.3. mu. g h−1mg−1And a faraday efficiency FE of 19.2%.
Description
Technical Field
The invention relates to the technical field of nitrogen reduction, in particular to a high-efficiency iron-molybdenum-based nitrogen reduction electrocatalyst and a preparation method thereof.
Background
In modern society, the problems of energy consumption and environment are getting more serious, and the development of new energy with simple operation, low pollution and low consumption is concerned. Ammonia gas (NH)3) Has high energy, high density and reproducibility, and is very potential. Ammonia is widely used in one of the most productive inorganic compounds in the fields of plastics, metallurgy, medicine, national defense and other industries, and about 80% of ammonia is used in agricultural production of chemical fertilizers, such as nitrogenous fertilizer, ammonia water, liquid ammonia, HNO3Ammonium salts, soda ash, and the like. At present, the industrial synthesis process of ammonia is still a Haber process requiring high temperature and high pressure, but the Haber process has large energy consumption and CO2The emission is high, and a new method for synthesizing ammonia is urgently needed to be developed to reduce energy consumption and improve yield.
In the aspect of biological nitrogen fixation, nitrogen fixation microorganisms mainly utilize nitrogen fixation enzyme to realize N2To NH3In which FeMoS is a key active site in the nitrogen fixation process as an active substance in the nitrogen fixation enzyme. Based on the research of FeMoS-based nitrogen fixation enzyme, several Fe and Mo-based catalysts are recently developed and used as nitrogen fixation catalysts, and the synthesis of FeS/MoS is reported in the literature2The NRR was catalyzed and the ammonia yield was 8.5. mu. g h at a voltage of-0.5V (vs. standard hydrogen electrode)−1cm−2The catalytic efficiency did not reach expectations. This may be due to FeS/MoS2The heterojunction structure of (a) prevents a truly co-catalytic nitrogen reduction of Fe and Mo. FeMoO has also been reported in the literature4As NRR catalyst, the ammonia yield was 45.8. mu. g h at a voltage of-0.5V (vs. standard hydrogen electrode)−1mg−1. . However, NH3The yield is not ideal and needs to be further improved. In order to better simulate the FeMoS synergistic effect in azotase, a special compound combining Fe, Mo and S elements is designed, and the research is not carried out so far. Therefore, the invention develops an efficient iron-molybdenum-based nitrogen fixation catalyst and a preparation method thereofProve FeMo3S4Is an efficient and stable NRR electrocatalyst.
The invention provides a nano-rod-shaped high-efficiency catalyst containing the combined action of Fe, Mo and S. Prepared FeMo3S4The special structure of the nano rod can provide more adsorption sites for the electrochemical adsorption of nitrogen, and the special synergistic effect of various atoms can better play a catalytic role. The iron-molybdenum-based nitrogen reduction catalyst improves the catalytic activity for nitrogen reduction and provides a new direction for electrocatalysis nitrogen fixation.
Disclosure of Invention
The invention aims to provide a high-efficiency iron-molybdenum-based nitrogen reduction electrocatalyst and a preparation method thereof. In order to solve the problems, the technical scheme of the invention is as follows:
1. an efficient iron-molybdenum-based nitrogen reduction electrocatalyst and a preparation method thereof are disclosed, and the preparation method comprises the following steps: (1) adding an iron-containing element reagent into distilled water to prepare an iron-containing pre-reaction liquid, uniformly stirring, carrying out hydrothermal reaction, naturally cooling to room temperature, centrifuging, washing, and carrying out vacuum drying to obtain iron-containing precursor nano powder; (2) placing the iron-containing precursor nano powder, a molybdenum source and a sulfur source reagent in a high-pressure kettle for hydro-thermal treatment, naturally cooling to room temperature, centrifuging, washing and vacuum drying to finally obtain precipitates containing iron, molybdenum and sulfur; (3) the precipitate containing iron, molybdenum and sulfur is finally obtained and is subjected to heat treatment in a tube furnace to obtain FeMo3S4And (4) nanorods.
2. In the step (1), iron source reagents comprise ferric trichloride hexahydrate, ferric nitrate nonahydrate, ferric acetate and ferric sulfate, and the optimal ferric trichloride hexahydrate; wherein the concentration of the iron-containing pre-reaction solution is 0.1 mug mL−1～1.0 μg mL−1The optimum concentration is 0.1. mu.g mL−1～0.3 μg mL−1。
3. In the step (1), the temperature of hydrothermal treatment is 140-240 ℃, the hydrothermal time is 18-48 h, the optimal temperature of hydrothermal treatment is 160-200 ℃, and the hydrothermal time is 18-28 h.
4. In the step (2), molybdenum source reagents comprise ammonium molybdate and sodium molybdate, and the optimal molybdenum source reagent is sodium molybdate; wherein the concentration of the molybdenum source reaction solution is 0.1 mug mL−1～1.0 μg mL−1The optimum concentration is 0.1. mu.g mL−1～0.4 μg mL−1。
5. In the step (2), the sulfur source reagent comprises thioacetamide, thiourea and sodium sulfide, and the optimal thioacetamide is adopted; wherein the concentration of the sulfur source reaction solution is 0.1 mug mL−1～1.0μg mL−1The optimum concentration is 0.2. mu.g mL−1～1.0 μg mL−1。
6. In the step (2), the molar ratio of precipitates containing iron, molybdenum and sulfur is 1-3: 1-4: 2-5, and the optimal molar ratio is 1-2: 2-4: 3 to 5.
7. In the step (2), the temperature of hydrothermal treatment is 140-240 ℃, the hydrothermal time is 18-48 h, the optimal temperature of hydrothermal treatment is 180-220 ℃, and the hydrothermal time is 24-48 h.
8. In the step (3), the finally obtained precipitate containing iron, molybdenum and sulfur is subjected to thermal annealing in a tube furnace argon atmosphere, wherein the annealing temperature is 300-800 ℃, the annealing time is 2-10 h, the optimal annealing temperature is 300-600 ℃, and the annealing time is 2-6 h.
9. The efficient iron-molybdenum-based nitrogen reduction electrocatalyst is characterized in that the electrocatalytic nitrogen reduction performance test is carried out on an electrochemical workstation, and a three-electrode system is used for testing so as to coat FeMo3S4The carbon paper of the nano-rod is a working electrode, the carbon rod is a counter electrode, and the Ag/AgCl electrode is a reference electrode; taking 0.1 mol/L sodium sulfate solution as electrolyte; an H-shaped glass electrolytic tank is used as an electrolytic reaction device.
Detailed Description
For a further understanding of the present invention, reference will now be made to the preferred embodiments of the present invention by way of example only, and to the accompanying drawings, which are included to further illustrate features and advantages of the present invention and are not intended to limit the scope of the present invention as set forth in the following claims.
Example one
The first step is as follows: 2.03 g ferric chloride hexahydrate is stirred and dissolved into 50 ml of distilled water, the solution is transferred into a 100 ml stainless steel autoclave with a polytetrafluoroethylene lining, the solution is respectively heated in a 160 ℃ oven for 16 h, the solution is naturally cooled to the room temperature, the iron-containing precursor nano powder is collected and precipitated by a centrifugal method, and then the precipitate is placed into a 60 ℃ oven for drying.
The second step is that: 0.18 g of iron-containing precursor nano powder, 1.45 g of sodium molybdate and 0.6 g of thioacetamide are prepared into a mixed suspension containing iron, molybdenum and sulfur in 50 ml of distilled water to be subjected to hydrothermal treatment for 24 hours at 220 ℃, the mixed suspension is naturally cooled to room temperature, and then the precipitate is collected by washing and centrifuging with distilled water and alcohol for many times, and is dried in a 60 ℃ oven in vacuum to finally obtain the precipitate containing iron, molybdenum and sulfur.
The third step: carrying out thermal annealing on the precipitate containing iron, molybdenum and sulfur in an Ar atmosphere in a tube furnace at 300 ℃ for 2 h to obtain FeMo3S4And (4) nanorods.
The fourth step: for the obtained FeMo3S4And (4) carrying out NRR performance test on the nanorod catalyst. 10 mg of FeMo is weighed3S4Adding 50 mu L Nafion solution into mixed solvent of nano rod powder, 960 mu L ethanol and water (1: 1), carrying out ultrasonic treatment for 1H to obtain uniform dispersion liquid, taking 20 mu L of the dispersion liquid, dropwise coating the dispersion liquid on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1cm × 1cm, naturally airing the carbon paper to be used as a working electrode, adopting a three-electrode standard system on an electrochemical workstation, using an electrolyte as 0.1 mol/L sodium sulfate solution and an H-type glass electrolytic tank as a reaction device, and testing the stability and durability of the NRR catalytic activity and NH by cyclic voltammetry, time current curve, impedance spectrum and the like3Yield and faradic efficiency.
Example two
The difference is that 2.03 g of ferric chloride hexahydrate are replaced by 3 g of ferric sulphate in the first step; hydrothermal treatment at 160 ℃ for 16 h was replaced by hydrothermal treatment at 180 ℃ for 24 h.
EXAMPLE III
As in example one, except that 2.03 g of ferric chloride hexahydrate was replaced with 3.03 g of ferric nitrate nonahydrate in the first step; hydrothermal treatment at 160 ℃ for 16 h was replaced by hydrothermal treatment at 200 ℃ for 28 h.
Example four
As in example one, except that 1.45 g of sodium molybdate was replaced with 1.06 g of ammonium molybdate in the second step; hydrothermal treatment at 220 ℃ for 24 h was replaced by hydrothermal treatment in a 220 ℃ oven for 32 h.
EXAMPLE five
As in example one, except that 0.6 g of thioacetamide in the second step was replaced with 0.6 g of sodium sulfate; hydrothermal treatment at 220 ℃ for 24 h was replaced by hydrothermal treatment in a 240 ℃ oven for 48 h.
EXAMPLE six
As in example one, except that in the third step the thermal annealing in Ar atmosphere for 2 h in a 300 ℃ tube furnace was replaced by thermal annealing in Ar atmosphere for 2 h in a 500 ℃ tube furnace.
The FeMo is obtained by hydrothermal and heat treatment3S4Is an efficient and stable NRR electrocatalyst. FeMo3S4The catalyst material improves the catalytic activity on NRR through multi-element synergistic effect. FeMo prepared by the invention3S4The nano-rods provide a new direction for electrocatalysis nitrogen fixation.
Claims (7)
1. An efficient iron-molybdenum-based nitrogen reduction electrocatalyst and a preparation method thereof are characterized in that the preparation method comprises the following steps: (1) adding an iron source reagent into distilled water to prepare iron-containing pre-reaction liquid, uniformly stirring, carrying out hydrothermal reaction, naturally cooling to room temperature, centrifuging, washing, and carrying out vacuum drying to obtain iron-containing precursor nano powder; (2) placing the iron-containing precursor nano powder, a molybdenum source and a sulfur source reagent in a high-pressure kettle for hydrothermal treatment, and naturallyCooling, centrifuging, washing and vacuum drying to finally obtain precipitate containing iron, molybdenum and sulfur; (3) the precipitate containing iron, molybdenum and sulfur is finally obtained and is subjected to heat treatment in a tube furnace to obtain FeMo3S4And (4) nanorods.
2. The high-efficiency Fe-Mo-N reduction electrocatalyst and its preparation method as claimed in claim 1, wherein in step (1), the iron source reagents are ferric trichloride hexahydrate, ferric nitrate nonahydrate, ferric sulfate, and the concentration of iron in the pre-reaction solution containing iron is 0.1 μ g mL−1～1.0 μg mL−1。
3. The high-efficiency Fe-Mo-based N reduction electrocatalyst and its preparation method as claimed in claim 1, wherein in step (1) (2), the temperature range of hydrothermal treatment is 140 ℃ to 240 ℃ and the hydrothermal time range is 18 h to 48 h.
4. The high efficiency iron-molybdenum-based nitrogen reduction electrocatalyst and the preparation method thereof according to claim 1, wherein in the step (2), the molybdenum source reagent is ammonium molybdate and sodium molybdate, and the sulfur source reagent is thioacetamide, thiourea or sodium sulfide.
5. The high-efficiency Fe-Mo-based N reduction electrocatalyst and the preparation method thereof according to claim 1, wherein in the step (2), the molar ratio of Fe-containing precipitates, Mo-containing precipitates and S-containing precipitates is 1-3: 1-4: 2 to 5.
6. The high-efficiency Fe-Mo-based N reduction electrocatalyst and the preparation method thereof according to claim 1, wherein in the step (3), the final precipitate containing Fe, Mo and S is subjected to thermal annealing in a tube furnace argon atmosphere, the annealing temperature range is 300-800 ℃, and the annealing time is 2-10 h.
7. Efficient iron-molybdenum-based nitrogen reduction electrocatalyst and preparation thereofThe method is characterized in that the electrocatalytic nitrogen reduction performance test is carried out on an electrochemical workstation, and the test is carried out by using a three-electrode system to coat FeMo3S4The carbon paper of the nano-rod is a working electrode, the carbon rod is a counter electrode, and the Ag/AgCl electrode is a reference electrode; taking 0.1 mol/L sodium sulfate solution as electrolyte; an H-shaped glass electrolytic tank is used as an electrolytic reaction device.
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