CN112007660A - Flower cluster-shaped FeS2Preparation method and application of @ C nitrogen fixation catalyst - Google Patents
Flower cluster-shaped FeS2Preparation method and application of @ C nitrogen fixation catalyst Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 229910052960 marcasite Inorganic materials 0.000 claims abstract description 19
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 36
- 229910021529 ammonia Inorganic materials 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910001414 potassium ion Inorganic materials 0.000 description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 description 8
- 235000011151 potassium sulphates Nutrition 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000004178 biological nitrogen fixation Methods 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 102000008857 Ferritin Human genes 0.000 description 1
- 238000008416 Ferritin Methods 0.000 description 1
- 108050000784 Ferritin Proteins 0.000 description 1
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/23—
-
- B01J35/33—
-
- 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
-
- 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
Abstract
The invention discloses a flower cluster-shaped FeS2The preparation method and the application of the @ C nitrogen fixation catalyst comprise the following steps: dissolving ferric trichloride hexahydrate, 1,3, 5-trimesic acid and polyvinylpyrrolidone K30(PVP) in an aqueous solution, performing ultrasonic treatment to form a uniform solution, adding the solution into a reaction kettle, reacting at 130 ℃ for 72 hours, cooling to room temperature, centrifuging, washing and drying to obtain an MIL-100(Fe) @ PVP precursor; adding MIL-100(Fe) @ PVP and thiourea into a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, cooling to room temperature, and then carrying out sulfuric acid and separationRespectively washing the seed water and drying to obtain FeS2@ C composite material. The method has the advantages of simple operation, low cost and wide raw material acquisition. The catalyst is used for electrocatalysis nitrogen fixation under normal temperature and pressure, and has excellent electrocatalysis ammonia production activity.
Description
Technical Field
The invention belongs to the technical field of electrocatalysisA FeS domain, in particular2The preparation method of the @ C composite material and the application of the composite material in electrocatalytic nitrogen fixation.
Background
Ammonia is a basic chemical raw material and plays an important role in economic production. Ammonia can be used for producing chemical fertilizers, and nitrogen fertilizers and compound fertilizers are basically produced by taking ammonia as a raw material and are widely applied in agriculture. So far, the nitrogen fixation types can be divided into: high-energy nitrogen fixation, biological nitrogen fixation and industrial nitrogen fixation. High-energy nitrogen fixation is mainly formed by promoting ammonia formation by high energy generated by lightning in nature, biological nitrogen fixation is performed by utilizing biological action of certain organisms or a bionic technology, and industrial nitrogen fixation is mainly performed by a Haber-Bosch process to produce ammonia. The Haber-Bosch process requires the reaction under high temperature and high pressure (350 ℃ F. 550 ℃ C., 150 ℃ C. 350atm), consumes high energy and pollutes the environment. In view of the shortage of fossil fuels and global climate change, it is important to explore catalytic reactions that produce ammonia under mild conditions.
Electrocatalytic nitrogen fixation, which is proven to be performed under mild conditions in recent years, is a potential ammonia synthesis alternative technology. The main problems faced by the current electrocatalytic ammonia synthesis are low ammonia production efficiency and Faraday efficiency, which are mainly because the reaction of nitrogen and hydrogen is very difficult to perform in reaction kinetics due to the fact that nitrogen-nitrogen triple bonds in nitrogen are very firm under normal temperature and normal pressure, and because the hydrogen evolution potential is very close to the nitrogen reduction potential, the efficiency of synthesizing ammonia by reducing nitrogen is severely restricted by the hydrogen evolution reaction as a competitive reaction, so that finding a balance point in the nitrogen reduction and hydrogen evolution reaction is helpful for promoting the electrocatalytic nitrogen fixation. In biological nitrogen fixation, ferritin and ferromolybdenum of azotase catalyze the nitrogen fixation reaction, so that the simulated azotase utilizes iron element and molybdenum element to catalyze nitrogen fixation electrically, which may possibly achieve good effect. In recent years, many studies have been made on nitrogen-fixing catalysts containing iron and molybdenum, but there is still a need to improve the ammonia yield and the faradaic efficiency.
The MOFs material refers to a periodic crystal porous material with a network structure formed by self-assembly of metal ions and organic ligands. It has the advantages of high porosity, regular pore channels, large specific surface area and the like. Because the MOFs material has the advantages, the nitrogen fixation performance of the compound prepared by using the MOFs material as a precursor can be improved. At present, researchers load metal nanoparticles on MOFs materials to carry out photocatalytic nitrogen fixation research, and the research finds that the adsorption of the MOFs materials on nitrogen and the thermal electron effect of the metal nanoparticles synergistically promote the photocatalytic nitrogen fixation, so that the MOFs materials have good application value in the electrocatalytic nitrogen fixation.
Disclosure of Invention
The invention aims to provide FeS synthesized by MIL-100(Fe) @ PVP and thiourea by a hydrothermal method2The @ C composite material is used for electrocatalytic nitrogen fixation.
The invention relates to FeS for electrocatalytic nitrogen fixation2The catalyst is made of composite material FeS coated with carbon cloth2@ C, the synthesis of the working electrode is carried out according to the following steps:
firstly, preparing MIL-100(Fe) @ PVP: dissolving ferric trichloride hexahydrate, 1,3, 5-trimesic acid and polyvinylpyrrolidone K30(PVP) in an aqueous solution, and performing ultrasonic treatment to form a uniform solution. And then adding the solution into a reaction kettle, reacting for a period of time at a certain temperature, cooling to room temperature, centrifuging, washing, and drying in vacuum to obtain MIL-100(Fe) @ PVP.
II, FeS2Preparation of @ C composite: adding MIL-100(Fe) @ PVP and thiourea into deionized water according to a certain mass ratio, stirring for 3 hours, adding into a reaction kettle, reacting at a certain temperature for a period of time, cooling to room temperature, centrifuging, washing, and drying in vacuum to obtain FeS2@C。
Thirdly, preparing a working electrode: grinding the composite material, and taking a certain amount of FeS2@ C composite material, added to an aqueous solution containing isopropanol and nafion, and subjected to ultrasonication. And (3) dripping a proper amount of uniformly mixed solution on the activated carbon cloth, and standing.
The mass ratio of ferric trichloride hexahydrate, 1,3, 5-trimesic acid and polyvinylpyrrolidone K30 in the step one is 37.8:27.2: 1;
the reaction temperature in the step one is 130 ℃, and the reaction time is 72 hours;
the washing mode in the first step is as follows: centrifugally washing the obtained product with anhydrous ethanol and deionized water for 3 times respectively;
the vacuum drying temperature in the first step is 60 ℃;
the mass ratio of MIL-100(Fe) @ PVP to thiourea in the step two is 1: 4;
the reaction temperature in the second step is 200 ℃, and the reaction time is 24 hours;
the washing mode in the second step is as follows: the obtained samples were used in an amount of 0.5mol L each–1Centrifugally washing with sulfuric acid and deionized water for 3 times;
the vacuum drying temperature in the second step is 60 ℃;
FeS in step three2The mass of the @ C composite material is 10mg, the volume of isopropanol is 0.75ml, the volume of nafion solution is 0.05ml, and the volume of deionized water is 2.2 ml;
in the third step, the ultrasonic time is 1.5 hours, and the standing time is 8 hours.
The method comprises the steps of carrying out X-ray powder diffraction, scanning electron microscopy, amperometric response method, linear scanning voltammetry, ultraviolet-visible spectrophotometry and the like on the FeS2The @ C material is subjected to characterization and electrochemical performance testing.
The invention has the advantages and effects that:
the method is simple to operate, MIL-100(Fe) @ PVP precursor is synthesized by a one-step hydrothermal method, and then sulfuration is carried out to generate FeS with a flower cluster-shaped structure consisting of nanosheets of 30-60nm2@ C material. The flower cluster structure can increase the surface area of the substance, thereby improving the exposure of active sites, fully contacting the catalyst with electrolyte, promoting the electron transfer and increasing the catalytic activity of the catalyst. The material is based on the special framework structure characteristics of MOFs, active sites are fully exposed, and a large number of iron element active sites promote nitrogen reduction. FeS2The @ C catalyst has excellent electrocatalytic nitrogen fixation performance, and the ammonia yield is 38.02 mu g h under the voltage of-0.6V in the electrocatalytic nitrogen fixation reaction-1mgcat. -1Faraday efficiencyThe content was 27.6%. The invention has simple process, easily obtained materials and lower cost, and is beneficial to industrial production.
Description of the drawings:
FIG. 1 shows a composite FeS2X-ray powder diffraction pattern of @ C;
FIG. 2 shows FeS as a composite material2@ C scanning electron microscope pictures;
FIG. 3 is FeS2@ C catalyst Potassium sulfate solution at pH 3.5 (1.0mol L)–1Potassium ion) to carry out nitrogen fixation reaction, and a time-current diagram of the catalyst under different voltages;
FIG. 4 shows FeS2@ C catalyst Potassium sulfate solution at pH 3.5 (1.0mol L)–1Potassium ion) and after different voltage reactions, the ultraviolet visible light absorption spectrogram of each electrolyte;
FIG. 5 shows FeS2@ C catalyst Potassium sulfate solution at pH 3.5 (1.0mol L)–1Potassium ion) to carry out nitrogen fixation reaction, and an ammonia yield chart under different voltages;
FIG. 6 shows FeS2@ C catalyst Potassium sulfate solution at pH 3.5 (1.0mol L)–1Potassium ion) and faradaic efficiency plots at different voltages.
The specific implementation mode is as follows:
(1) 1.89g of ferric chloride hexahydrate, 1.36g of 1,3, 5-trimesic acid and 0.05g of polyvinylpyrrolidone K30 were dissolved in 50mL of an aqueous solution and sonicated to form a homogeneous solution. And then adding the solution into a reaction kettle, reacting for 72 hours at 130 ℃, cooling to room temperature, respectively centrifugally washing for 3 times by using absolute ethyl alcohol and deionized water, and drying in vacuum at 60 ℃ to obtain an MIL-100(Fe) @ PVP precursor.
(2) Adding 0.1g MIL-100(Fe) @ PVP and 0.4g thiourea into 50ml deionized water, stirring for 3 hours, placing into a reaction kettle, performing hydrothermal reaction at 200 ℃ for 24 hours, cooling to room temperature, and adding 0.5mol L of solution–1Respectively centrifugally washing with sulfuric acid and deionized water for 3 times, and vacuum drying at 60 deg.C for 12 hr to obtain FeS2@ C composite material.
(3) Putting the carbon cloth into an acetone solution, absolute ethyl alcohol and a deionized water solution in sequence,and respectively carrying out ultrasonic treatment for 30 minutes, then washing the carbon cloth with water, then putting the carbon cloth into a reaction kettle, adding concentrated nitric acid, and activating for 1 hour at 120 ℃. Drying the activated carbon cloth, and cutting into square blocks of 1cm multiplied by 1 cm. 10mg of FeS was taken2@ C was added to 2.2ml of deionized water containing 0.75ml of isopropyl alcohol and 0.05ml of nafion solution, sonicated for 1.5 hours, and then the sonicated homogeneous material was drop coated onto a carbon cloth to form a coating containing 0.3mg/cm2A working electrode of a catalyst.
The material FeS is shown in FIG. 12X-ray powder diffraction Pattern of @ C, corresponding to FeS2Standard card of (JCPDS, No. 42-1340). As shown in the figure, diffraction peaks 2 θ of 28.5 °, 33.1 °, 37.1 °, 40.8 °, 47.4 °, 56.3 ° and 64.3 ° correspond to FeS, respectively2The (111), (200), (210), (211), (220), (311), and (321) crystal planes of the phases. The obtained diffraction peak is matched with the characteristic diffraction peak in the standard card, which indicates that the material contains FeS2。
The material FeS is shown in FIG. 22The scanning electron microscope image of @ C shows that the obtained material is a flower cluster-shaped structure composed of 30-60nm nanosheets, and the porous structure has a high specific surface area, so that the catalyst is in full contact with the electrolyte.
In FIG. 3, the material FeS2@ C Potassium sulfate solution at pH 3.5 (1.0mol L)–1Potassium ion) under-0.4V, -0.5V, -0.6V and-0.7V, respectively, and shows that the current density of the material increases with increasing voltage.
FIG. 4 shows FeS as a material2@ C Potassium sulfate solution at pH 3.5 (1.0mol L)–1Potassium ion) and after the reaction is finished, carrying out ultraviolet visible spectrophotometry on the electrolyte to measure the absorbance of the solution. As can be seen from the graph, the absorbance increased first and then decreased as the voltage increased, and the absorbance was highest at a voltage of-0.6V.
FIG. 5 shows FeS2@ C catalyst Potassium sulfate solution at pH 3.5 (1.0mol L)–1Potassium ion) and electrocatalysis is carried out on the nitrogen fixation reaction under different reaction voltages to fix the ammonia yield of nitrogen. As can be seen, the ammonia yield increases and then decreases with increasing voltage, atThe highest ammonia yield can reach 38.02 mu g h under the voltage of-0.6V-1mgcat. -1。
In FIG. 6, FeS is shown2@ C catalyst Potassium sulfate solution at pH 3.5 (1.0mol L)–1Potassium ion) and electrocatalysis nitrogen fixation faradaic efficiency under different reaction voltages. As can be seen from the figure, the Faraday efficiency firstly increases and then decreases along with the increase of the voltage, and the Faraday efficiency is highest under the voltage of-0.6V and can reach 27.6 percent.
In conclusion, the invention successfully synthesizes FeS with a flower cluster structure consisting of nanosheets of 30-60nm by using a hydrothermal method and utilizing ferric trichloride hexahydrate, 1,3, 5-trimesic acid, polyvinylpyrrolidone K30 and thiourea as reactants2@ C material. The material has the ammonia yield of 38.02 mu g h under the voltage of-0.6V in the electrocatalytic nitrogen fixation reaction-1mgcat. -1The Faraday efficiency was 27.6%.
Claims (8)
1. Flower cluster-shaped FeS2The preparation method of the @ C nitrogen fixation catalyst comprises the following steps:
(1) dissolving ferric trichloride hexahydrate, 1,3, 5-trimesic acid and polyvinylpyrrolidone K30(PVP) in an aqueous solution, performing ultrasonic treatment to form a uniform solution, then reacting the solution in a reaction kettle at 130 ℃ for 72 hours, cooling to room temperature, centrifuging, washing and drying to obtain an MIL-100(Fe) @ PVP precursor;
(2) adding MIL-100(Fe) @ PVP and thiourea into deionized water, stirring uniformly, adding into a reaction kettle, performing hydrothermal reaction at 200 ℃ for 24 hours, cooling to room temperature, washing with sulfuric acid and deionized water respectively, and drying to obtain FeS2@ C composite material.
2. The FeS of claim 12The preparation method of the @ C composite material is characterized in that the mass ratio of the ferric trichloride hexahydrate, the 1,3, 5-trimesic acid and the polyvinylpyrrolidone K30 in the step (1) is 37.8:27.2: 1.
3. The FeS of claim 12@ C composite materialThe preparation method is characterized in that the reaction temperature in the step (1) is 130 ℃, and the reaction time is 72 hours.
4. The FeS of claim 12The preparation method of the @ C composite material is characterized in that the washing in the step (1) is as follows: respectively centrifugally washing the product for 3 times by using absolute ethyl alcohol and deionized water; the drying is carried out for 12 hours under vacuum at 60 ℃.
5. The FeS of claim 12The preparation method of the @ C composite material is characterized in that the mass ratio of MIL-100(Fe) @ PVP to thiourea in the step (2) is 1: 4.
6. The FeS of claim 12The preparation method of the @ C composite material is characterized in that the reaction temperature in the step (2) is 200 ℃, and the reaction time is 24 hours.
7. The FeS of claim 12The preparation method of the @ C composite material is characterized in that the washing in the step (2) is as follows: the obtained products are respectively used for 0.5mol L–1Centrifugally washing with sulfuric acid and deionized water for 3 times; the drying is carried out for 12 hours under vacuum at 60 ℃.
8. The FeS of claim 12The application of the @ C material is applied to electrocatalytic nitrogen fixation reaction at normal temperature and normal pressure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113201758A (en) * | 2021-04-08 | 2021-08-03 | 哈尔滨理工大学 | FeS2Preparation method and application of @ GO nitrogen fixation catalyst |
| CN113736470A (en) * | 2021-09-15 | 2021-12-03 | 昆明理工大学 | Method for preparing mining area soil conditioner from wet sludge in alpine and high-altitude areas |
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