CN112007661A - Preparation and application of nitrogen fixation catalyst FeMoO4/FeS2@ C - Google Patents
Preparation and application of nitrogen fixation catalyst FeMoO4/FeS2@ C Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052960 marcasite Inorganic materials 0.000 title claims abstract description 39
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 28
- 229910015142 FeMoO4 Inorganic materials 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 229910020881 PMo12O40 Inorganic materials 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 7
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000013144 Fe-MIL-100 Substances 0.000 claims description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910001414 potassium ion Inorganic materials 0.000 description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 description 6
- 235000011151 potassium sulphates Nutrition 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000000634 powder X-ray diffraction 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004178 biological nitrogen fixation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- 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
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention provides FeMoO for catalytically synthesizing ammonia at normal temperature and normal pressure4/FeS2A @ C composite catalyst and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: FeCl is added3·6H2O、H3PMo12O40Dissolving polyvinylpyrrolidone K30(PVP) in deionized water, adding 1,3, 5-trimesic acidInto the above solution. Then, adding the uniformly mixed solution into a reaction kettle, carrying out hydrothermal reaction at 160-200 ℃, and carrying out centrifugal washing to obtain MIL-100(Fe) @ PMo12@ PVP. Then, MIL-100(Fe) @ PMo12Putting @ PVP and thiourea into a reaction kettle for reaction, centrifuging, washing and drying the obtained sample to obtain FeMoO4/FeS2@ C material. The preparation method is simple, convenient and quick, and can be completed in two steps; the obtained composite catalyst has high-efficiency electrocatalytic nitrogen fixation performance.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to FeMoO4/FeS2The preparation method of the @ C composite material and the application of the composite material in electrocatalytic nitrogen fixation.
Background
Ammonia is one of the most important resources in the world and is an important raw material in chemical production, most of synthetic ammonia is used as an industrial raw material for synthesizing fertilizers, and the synthesis of ammonia is indispensable to both human beings and the earth ecosystem. Currently, as the times advance, the population increases more rapidly, and the demand for ammonia increases. In the atmosphere, nitrogen accounts for about 78%, but converting nitrogen to ammonia is a major difficulty. Because of the strong and stable bond energy of nitrogen-nitrogen triple bond, the Haber-Bosch process of high-temperature and high-pressure reaction condition is used for ammonia synthesis in industry. However, the Haber-Bosch process consumes a lot of energy, releases a lot of greenhouse gases and is harmful to the environment, so that a method for synthesizing ammonia under a milder condition is urgently needed to be found.
In the nitrogen reduction reaction, various modes such as biological nitrogen fixation, photocatalysis nitrogen fixation, electrocatalysis nitrogen fixation and the like exist. The biological nitrogen fixation can be carried out nitrogen reduction under mild conditions, but is limited to a small amount of leguminous plants and microorganisms which can directly convert nitrogen in the air into substances required by the microorganisms. In the electrocatalysis nitrogen fixation, the electron supply is stable, the utilization rate is high, the chemical reaction direction and the reaction speed are easy to control, and the method is a relatively green and efficient process method. However, nitrogen-nitrogen triple bond energy of nitrogen is high, the nitrogen is not easy to break, and the reaction of nitrogen and hydrogen is difficult to perform on reaction kinetics, so that the research on how to improve the Faraday efficiency and the ammonia yield of the electrocatalytic nitrogen fixation under normal temperature and pressure is the key point of research.
Metal organic framework Materials (MOFs) are a new class of stable hybrid inorganic-organic materials that regulate and modify catalytic reactions by rationally combining organic bridging ligands and metal ions with well-defined coordination geometries. MOFs have highly ordered pore channels, the derived nano material has a stable mechanical nano structure and adjustable active sites, and the unique crystal and porous structure make the MOFs become templates and precursors for synthesizing some catalysts, so that the MOFs have more applications in the fields of adsorption, catalysis, drug delivery, ion exchange and the like. The polyoxometallate is a metal oxygen cluster with nanometer size and different negative charges, contains a large amount of transition metal elements, has catalytic action on a plurality of reactions, has good structural diversity and adjustability, and can be used as counter ions to exist in pore channels of MOFs or be coordinated with the MOFs to form a composite material. Based on the advantages of the polyoxometallate and the metal organic framework material, the application of the polyoxometallate and the metal organic framework material in electrocatalytic nitrogen fixation has potential advantages.
Disclosure of Invention
The invention aims to provide a hydrothermal method for mixing MIL-100(Fe) and H3PMo12O40Compounding and then vulcanizing to synthesize FeMoO4/FeS2The @ C composite material is used for electrocatalytic nitrogen fixation.
The invention relates to FeMoO for electrocatalytic nitrogen fixation4/FeS2The @ C composite material catalyst is characterized in that the working electrode is made of carbon cloth and composite material FeMoO coated on the carbon cloth4/FeS2@ C, the composition of the working electrode is as follows:
one, MIL-100(Fe) @ PMo12Preparation of @ PVP: FeCl is added3·6H2O、H3PMo12O40And polyvinylpyrrolidone K30(PVP) in deionized water, adding 1,3, 5-trimesic acid into the solution, and performing ultrasonic treatment to obtain a uniform solution. And then, adding the uniformly mixed 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. MIL-100(Fe) @ PMo is obtained12@ PVP precursor.
Two, FeMoO4/FeS2Preparation of @ C composite: mixing MIL-100(Fe) @ PMo12Adding @ PVP and thiourea into deionized water according to a certain mass ratio, stirring for 3 hours, adding into a reaction kettle, and reacting at a certain temperatureCooling to room temperature, centrifuging, washing, and vacuum drying. To obtain FeMoO4/FeS2@ C material.
Thirdly, preparing a working electrode: grinding the composite material, and taking a certain amount of FeMoO4/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.
FeCl as described in step one3·6H2O、H3PMo12O40The mass ratio of the 1,3, 5-trimesic acid to the polyvinylpyrrolidone K30(PVP) is 37.8:27:27.2: 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 ℃;
MIL-100(Fe) @ PMo in the second step12The mass ratio of @ PVP to thiourea 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 products are respectively used for 0.5mol L–1Centrifugally washing with sulfuric acid and deionized water for 3 times;
the vacuum drying temperature in the second step is 60 ℃;
FeMoO in step III4/FeS2The 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 is used for treating the FeMoO by methods such as X-ray powder diffraction, a scanning electron microscope, an ampere response method, a linear scanning voltammetry method, an ultraviolet visible spectrophotometry and the like4/FeS2The @ C material is subjected to characterization and electrochemical performance testing.
The invention has the advantages and effects that:
the invention uses a one-pot method to mix-100 (Fe) and PMo12Compounding, and using polyvinylpyrrolidone as dispersant to form MIL-100(Fe) @ PMo12@ PVP precursor, sulfurizing the precursor by hydrothermal method to obtain FeMoO4/FeS2@ C composite material. The material is a bulk material, and nanoparticles with the particle size of about 20nm are dispersed on the surface of the material, so that the contact area of the material and electrolyte can be increased, and the electron transmission is promoted. The invention combines iron and molybdenum elements to promote the electrocatalytic nitrogen fixation effect. FeMoO prepared by the invention4/FeS2The @ C catalyst has excellent electrocatalytic nitrogen fixation performance, and the ammonia yield is 51.0 mu g h under the voltage of-0.5V in the electrocatalytic nitrogen fixation reaction-1mgcat. -1The Faraday efficiency was 43.9%.
Description of the drawings:
FIG. 1 shows a composite FeMoO4/FeS2X-ray powder diffraction pattern of @ C;
FIGS. 2 and 3 are composite FeMoO4/FeS2@ C scanning electron microscope pictures;
FIG. 4 is FeMoO4/FeS2@ C catalyst Potassium sulfate solution at pH 3.5 (1.0mol L)–1Potassium ion) and after different voltage reactions, the ultraviolet-visible absorption spectrogram of each electrolyte;
FIG. 5 is FeMoO4/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 is FeMoO4/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 FeCl3·6H2O and 1.35g H3PMo12O40Dissolved in 50mL of aqueous solution and sonicated to form a homogeneous solution. Then 0.05g of polyvinylpyrrolidineAdding ketone K30 into the above solution, adding 1.36g 1,3, 5-trimesic acid, reacting at 130 deg.C for 72 hr, cooling to room temperature, centrifuging with anhydrous ethanol and deionized water for 3 times, and vacuum drying at 60 deg.C to obtain MIL-100(Fe) @ PMo12@ PVP precursor.
(2) 0.1g of MIL-100(Fe) @ PMo12@ 0.4g of thiourea and PVP are added into 50ml of deionized water, stirred for 3 hours, added into a reaction kettle, subjected to hydrothermal reaction at 200 ℃ for 24 hours, cooled to room temperature, and subjected to 0.5mol L–1Respectively centrifugally washing with sulfuric acid and deionized water for 3 times, and vacuum drying at 60 deg.C for 12 hr to obtain FeMoO4/FeS2@ C composite material.
(3) Sequentially putting the carbon cloth into an acetone solution, an absolute ethyl alcohol solution and a deionized water solution, performing ultrasonic treatment for 30 minutes respectively, washing the carbon cloth with water, 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. Taking 10mg of FeMoO4/FeS2@ 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 X-ray powder diffraction pattern of the material FeMoO4/FeS2@ C is shown in FIG. 1, corresponding to FeS2(JCPDS, No.42-1340) and FeMoO4(JCPDS, No. 22-1115). 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 had diffraction peaks 2 θ of 14.0 °, 18.6 °, and 25.3 ° corresponding to the (-110), (-201), and (-112) crystal planes of the FeMoO4 phase, respectively. The obtained diffraction peak is matched with the characteristic diffraction peak in the standard card, which indicates that the material is FeS2And FeMoO 4.
The material FeMoO is shown in FIGS. 2 and 34/FeS2The scanning electron microscope image of @ C shows that the obtained material is of a blocky structure, and nanoparticles with the size of about 20nm are dispersed on each block, so that the specific surface area is increased, and the contact area with the electrolyte can be increased。
FIG. 4 shows a potassium sulfate solution (1.0mol L) of the material FeMoO4/FeS2@ C at pH 3.5–1Potassium 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, the absorbance increased and then decreased with increasing voltage, and the absorbance was highest at-0.5V.
FIG. 5 is a potassium sulfate solution (1.0mol L) of FeMoO4/FeS2@ C catalyst at pH 3.5–1Potassium 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, and the highest ammonia yield can reach 51.0 mu g h at-0.5V-1mgcat. -1。
A potassium sulfate solution (1.0mol L) of FeMoO4/FeS2@ C catalyst at pH 3.5 is shown in FIG. 6–1Potassium ion) and electrocatalysis nitrogen fixation faradaic efficiency under different reaction voltages. As can be seen, the Faraday efficiency is increased and then decreased along with the increase of the voltage, and the Faraday efficiency is highest under the voltage of-0.5V and can reach 43.9 percent.
In summary, the present invention utilizes FeCl in hydrothermal method3·6H2O、H3PMo12O401,3, 5-trimesic acid, polyvinylpyrrolidone K30(PVP) and thiourea are taken as reactants to successfully synthesize FeMoO4/FeS2@ C material. The material has ammonia yield of 51.0 mu g h under the voltage of-0.5V in the electrocatalytic nitrogen fixation reaction-1mgcat. -1The Faraday efficiency was 43.9%.
Claims (8)
1. FeMoO for catalytic synthesis of ammonia at normal temperature and pressure4/FeS2The preparation method of the @ C composite catalyst comprises the following steps:
(1) FeCl is added3·6H2O、H3PMo12O40And polyvinylpyrrolidone K30(PVP) were dissolved in deionized water, and 1,3, 5-trimesic acid was added to the above solution. Subsequently, the uniformly mixed solution was added to a reaction vessel and reacted at 130 ℃ for 72 hours.Cooling to room temperature, centrifuging and washing with anhydrous ethanol and deionized water to obtain MIL-100(Fe) @ PMo12@PVP；
(2) Mixing MIL-100(Fe) @ PMo12@ PVP and thiourea were put in a reaction vessel and reacted at 200 ℃ for 24 hours. After cooling to room temperature, the obtained sample is respectively centrifugally washed by sulfuric acid and deionized water, and dried to obtain FeMoO4/FeS2@ C material.
2. The FeMoO of claim 14/FeS2The preparation method of the @ C composite material is characterized in that FeCl is adopted in the step (1)3·6H2O、H3PMo12O40The mass ratio of the 1,3, 5-trimesic acid to the polyvinylpyrrolidone K30 is 37.8:27:27.2: 1.
3. The FeMoO of claim 14/FeS2The preparation method of the @ C composite material is characterized in that the reaction temperature in the step (1) is 130 ℃, and the reaction time is 72 hours.
4. The FeMoO of claim 14/FeS2The preparation method of the @ C composite material is characterized in that the washing in the step (1) is to centrifugally wash the obtained product for 3 times by respectively using absolute ethyl alcohol and deionized water; the drying is carried out for 12 hours under vacuum at 60 ℃.
5. The FeMoO of claim 14/FeS2The preparation method of the @ C composite material is characterized in that the MIL-100(Fe)/PMo in the step (2)12The mass ratio of @ PVP to thiourea is 1: 4.
6. The FeMoO of claim 14/FeS2The 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 FeMoO of claim 14/FeS2The preparation method of the @ C composite material is characterized in that the products to be obtained by washing in the step (2) 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 FeMoO of claim 14/FeS2The application of the material of @ C is applied to electrocatalytic nitrogen fixation reaction at normal temperature and normal pressure.
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