CN111389400A - Preparation method of catalyst for fused salt electrochemical synthesis of ammonia - Google Patents
Preparation method of catalyst for fused salt electrochemical synthesis of ammonia Download PDFInfo
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- CN111389400A CN111389400A CN202010208384.1A CN202010208384A CN111389400A CN 111389400 A CN111389400 A CN 111389400A CN 202010208384 A CN202010208384 A CN 202010208384A CN 111389400 A CN111389400 A CN 111389400A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 150000003839 salts Chemical class 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000007833 carbon precursor Substances 0.000 claims abstract description 20
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 17
- 239000008103 glucose Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010963 304 stainless steel Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material 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
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
A method for preparing a catalyst for electrochemically synthesizing ammonia by molten salt. The method comprises the following specific steps: dissolving glucose and ferric nitrate in water to obtain a mixed solution, putting the mixed solution in a hydrothermal reaction kettle to synthesize a carbon precursor in a hydrothermal mode, centrifugally washing the carbon precursor by using deionized water, and drying the carbon precursor to obtain the carbon precursor; carbonizing the obtained carbon precursor under the protection of nitrogen, and naturally cooling to room temperature to obtain carbon spheres; weighing ferric nitrate according to a certain iron-carbon ratio, dissolving the ferric nitrate with 50ml of deionized water to prepare a solution, slowly adding 50g of carbon spheres into the solution under stirring, soaking for a certain time after uniformly stirring, drying, roasting in a muffle furnace, and naturally cooling to room temperature to obtain the catalyst. The method for preparing the catalyst has the advantages of easily available raw materials, low cost, simple operation, good controllability and easy large-scale mass production; the carbon spheres are adopted to load the ferric oxide catalyst, the molten NaOH-KOH is taken as electrolyte, the nitrogen and the water are taken as raw material gases, and the ammonia production rate and the coulombic efficiency of the electrochemical synthesis of ammonia are higher.
Description
Technical Field
The invention relates to a preparation method of a catalyst for electrochemically synthesizing ammonia.
Background
The synthetic ammonia industry plays a significant role in economic and social development, the global ammonia yield per year exceeds 1.5 hundred million tons, and the synthetic ammonia is mainly used for producing chemical fertilizers and chemical intermediates, and in addition, the ammonia also has the advantages of high hydrogen content (the mass ratio reaches 17.6 percent), high energy density, easy liquefaction and the like, and is expected to become an important clean hydrogen storage and energy storage material. The traditional Haber-Bosch process for ammonia synthesis is based on H over a commercial iron-based catalyst2And N2The method is synthesized at high temperature (400-600 ℃) and high pressure (20-40 MPa), the energy consumption is high due to harsh reaction conditions, the preparation of the required raw material hydrogen strongly depends on non-renewable fossil raw materials such as natural gas and coal, and a large amount of greenhouse gases such as carbon dioxide are discharged.
The electrochemical synthesis of ammonia by using water and nitrogen as raw materials spans the dependence of the traditional process on fossil energy, does not generate greenhouse gases, is a sustainable carbon-free green synthesis method of ammonia, and has great development potential and wide application prospect. The existing catalyst for electrochemically synthesizing ammonia mainly comprises noble metal catalysts which take Au, Ru, Pd and the like as active components, but the noble metal catalysts are high in cost and are unrealistic to be widely applied to industrial production, so that the development of non-noble metal catalysts is promoted. The non-noble metal catalyst for electrochemical synthesis of ammonia mainly takes oxides or sulfides of transition metals such as Fe, Mo and Sn as active components and takes carbon materials such as active carbon and carbon nano tubes as carriers. Although the price of the activated carbon is relatively low, the general graphitization degree is limited, so that the electronic conductivity of the activated carbon is limited; carbon nanotubes have excellent properties, but are currently a noble material in terms of price and ease of mass production. Therefore, it is very important to design a low-cost and practical high-efficiency electrocatalyst.
Disclosure of Invention
In order to solve the technical problems mentioned in the background technology, the invention provides a preparation method of a fused salt electrochemical synthesis ammonia catalyst, and the method for preparing the catalyst has the advantages of easily obtained raw materials, low cost, simple operation, good controllability and easy large-scale mass production; the carbon spheres are adopted to load the ferric oxide catalyst, the molten NaOH-KOH is taken as electrolyte, the nitrogen and the water are taken as raw material gases, and the ammonia production rate and the coulombic efficiency of the electrochemical synthesis of ammonia are higher.
The technical scheme of the invention is as follows: the preparation method of the catalyst for electrochemically synthesizing ammonia by using molten salt comprises the following specific steps:
dissolving glucose and ferric nitrate in water to obtain a mixed solution, putting the mixed solution into a hydrothermal reaction kettle to synthesize a carbon precursor in a hydrothermal mode, centrifugally washing the carbon precursor for multiple times by using deionized water, and drying the carbon precursor to obtain the carbon precursor;
in the step, the mass ratio of glucose to ferric nitrate in the mixed solution is 30: 1-30: 6, the concentration of glucose is 10-30 wt%, the hydrothermal synthesis temperature is 140-200 ℃, the hydrothermal synthesis time is 4-16 hours, and the drying temperature is 60-100 ℃;
secondly, carbonizing the carbon precursor obtained in the first step under the protection of nitrogen, and naturally cooling to room temperature to obtain carbon spheres; in the step, the carbonization temperature range is 300-700 ℃ and the carbonization time range is 2-5 hours;
thirdly, weighing ferric nitrate according to a certain iron-carbon ratio, dissolving the ferric nitrate with 50ml of deionized water to prepare a solution, taking 50g of the carbon spheres obtained in the second step, and slowly adding 50g of the carbon spheres into the solution prepared in the step under stirring; soaking for a certain time after uniformly stirring, and then drying; finally, roasting in a muffle furnace, and naturally cooling to room temperature to obtain a catalyst;
the range of the certain iron-carbon ratio in the step is 3: 50-9: 50; the dipping time ranges from 6 hours to 24 hours; the roasting temperature is 300-500 deg.c and the roasting time is 2-5 hr.
Preferably, in the first step, the mass ratio of glucose to ferric nitrate in the mixed solution is 30:3, the glucose concentration is 23 wt%, the hydrothermal synthesis temperature is 180 ℃, and the hydrothermal synthesis time is 8 hours; in the second step, the carbonization temperature is 500 ℃ and the carbonization time is 3 hours; in the third step, the iron-carbon ratio is 7:50, the impregnation time is 24 hours, the roasting temperature is 300 ℃, and the roasting time is 3 hours.
The invention has the advantages that (1) raw materials needed by the preparation of the catalyst are easy to obtain, the cost is low, the operation is simple, the controllability is good, and the large-scale mass production is easy, (2) the catalyst for electrochemically synthesizing ammonia prepared by the invention is carbon sphere loaded ferric oxide, the diameter distribution of the carbon sphere is uniform, the appearance is uniform, the diameter is about 5-10 mu m, the loaded ferric oxide particles are in an ellipsoid shape with the size of about 40 × 20 nm, (3) the carbon sphere loaded ferric oxide catalyst is adopted, molten NaOH-KOH is taken as electrolyte, nitrogen and water are taken as raw materials, and the ammonia production rate and the coulombic efficiency of electrochemically synthesizing ammonia can respectively reach 1.61 × 10-8mol•s-1•cm-2And 86.1 percent, has good application prospect. The term "coulombic efficiency" refers to the percentage of actual ammonia production compared to the electrochemical theory of ammonia production.
Description of the drawings:
FIG. 1 is the XRD pattern of the catalyst prepared in example 1;
FIG. 2 is an SEM photograph of the catalyst prepared in example 1;
FIG. 3 is a TEM photograph of the catalyst prepared in example 1;
FIG. 4 is a graph showing the current densities of the catalysts prepared in example 1 for ammonia synthesis at different electrolysis voltages;
FIG. 5 shows the ammonia production rate and coulombic efficiency for the synthesis of ammonia at different electrolysis voltages for the catalyst prepared in example 1;
FIG. 6 shows the stability of the catalyst prepared in example 1 for the electrochemical synthesis of ammonia.
The specific implementation mode is as follows:
the above-mentioned aspects of the present invention will be described in further detail by examples. Example 1:
(1) preparing an aqueous solution with the concentration of 23 wt% of glucose, weighing ferric nitrate according to the mass ratio of the glucose to the ferric nitrate of 10:1, dissolving the ferric nitrate in the aqueous solution of the glucose to obtain a mixed solution of the glucose and the ferric nitrate, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 8 hours at 180 ℃, carrying out centrifugal washing for multiple times by using deionized water after the hydrothermal reaction, and drying to obtain a carbon precursor;
(2) carbonizing the carbon precursor obtained in the step (1) for 3 hours at 500 ℃ under the protection of nitrogen, and naturally cooling to room temperature to obtain carbon spheres;
(3) weighing ferric nitrate according to the iron-carbon ratio =7:50, dissolving the ferric nitrate with 50ml of deionized water to prepare a solution, slowly adding 50g of carbon spheres into the solution under stirring, uniformly stirring, dipping for 24 hours, drying, roasting in a muffle furnace at 300 ℃ for 3 hours, naturally cooling to room temperature after roasting, and grinding to obtain the catalyst.
The prepared catalyst is added into molten 50% mol NaOH-50% mol KOH electrolyte, a nickel sheet is used as an anode (2 cm × 2.5 cm), a 304 stainless steel net (200 meshes, 2cm × 2.5 cm) is used as a cathode, wet nitrogen is blown to the cathode at the flow rate of 250ml/min, then a power supply is switched on, constant voltage electrolysis is carried out under certain voltage, and the ammonia generated by electrolysis is analyzed and measured.
The yield of the carbon precursor obtained in the step (1) in example 1 is 32 wt%, when the catalyst obtained in example 1 is analyzed by XRD, SEM and TEM, it can be seen from fig. 1 that the iron oxide as the active component supported by the carbon spheres is mainly ferric oxide and ferroferric oxide, as shown in the SEM photograph (fig. 2), the catalyst obtained is in the form of spheres with uniform morphology, the diameter of the carbon spheres is distributed in the range of 5-10 μm, and as shown in the TEM photograph (fig. 3), the iron oxide particles supported on the carbon spheres are uniformly distributed, and the particles are in the form of spheroids with the size of about 40 × 20 nm.
Application example 1 (electrocatalytic Synthesis of Ammonia Using the synthesized catalyst)
Taking a nickel sheet as an anode (2 cm × 2.5.5 cm), taking a 304 stainless steel net (200 meshes, 2cm × 2.5.5 cm) as a cathode, weighing 70g of a mixture of 50% molNaOH and 50% molKOH, fully grinding and uniformly mixing, then putting into a corundum crucible, putting the corundum crucible filled with electrolyte into an electric furnace, heating to 250 ℃, adding a catalyst when the electrolyte is fully molten, uniformly mixing with the electrolyte, then respectively placing the anode and the cathode, blowing wet nitrogen to the cathode at the flow rate of 250ml/min, switching on a power supply, and electrolyzing at constant voltage under a certain voltage, and using 500 ml of H with the concentration of 0.001 mol/L2SO4The absorption solution absorbs ammonia carried by nitrogen from the electrolytic cell, and the concentration of ammonia in the absorption solution is measured by a 722E type visible spectrophotometer at a wavelength of 697nm by a salicylic acid spectrophotometry (HJ 536-2009).
FIG. 4 is a graph showing current densities at different electrolysis voltages, which shows that the current densities rapidly decrease in the initial stage of electrolysis at different electrolysis voltages and then run at a steady current density as the electrolysis proceeds, indicating that a steady electrochemical reaction occurs on the catalyst, FIG. 5 is a graph showing ammonia production rates and coulombic efficiencies at different electrolysis voltages, the ammonia production rate increases with the increase in the electrolysis voltage, and a maximum ammonia production rate of 1.61 × 10 is obtained at 1.75V-8mol•s-1•cm-2(ii) a The coulombic efficiency can reach 86.1% at the highest when the voltage is 1.15V, and gradually decreases with the increase of the electrolytic voltage, which indicates that the electrolytic process has obvious reaction of water electrolysis and decomposition into hydrogen besides the electrochemical synthesis of ammonia, but the current efficiency is still up to 20.8% at 1.75V. Meanwhile, the prepared catalyst has good stability in electrochemical synthesis of ammonia (figure 6).
Comparative example: to illustrate the effect of adding ferric nitrate during hydrothermal synthesis, a control experiment of the hydrothermal synthesis step (1) in example 1) was performed, but it was different from step (1) in example 1 in that ferric nitrate was not added during preparation of the glucose solution. The yield of the carbon precursor obtained in this comparative example was only 8.7 wt%. The results show that the yield of the carbon precursor obtained when ferric nitrate is not added into the glucose solution in the hydrothermal synthesis is obviously reduced, the utilization rate of raw materials is very low, and the subsequent macro preparation of carbon spheres is not facilitated.
EXAMPLE 2 this example is different from example 1 in that the carbonization temperature in step (2) was 600 ℃ and the ammonia production rate in constant voltage electrolysis at 1.15V was 4.89 × 10 in the other steps similar to example 1-9mol•s-1•cm-2The coulombic efficiency was 61.2%.
EXAMPLE 3 this example is different from example 1 in that the iron-carbon ratio in step (3) was 9:50, and the ammonia production rate in constant-voltage electrolysis at 1.15V was 4.29 × 10-9mol•s-1•cm-2The coulombic efficiency was 17.3%.
EXAMPLE 4 this example is different from example 1 in that the calcination temperature in step (3) was 400 ℃ and the ammonia production rate in constant voltage electrolysis at 1.15V was 4.95 × 10 in the other steps similar to example 1-9mol•s-1•cm-2The coulombic efficiency was 27.3%.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (2)
1. A preparation method of a fused salt electrochemical synthesis ammonia catalyst comprises the following specific steps:
dissolving glucose and ferric nitrate in water to obtain a mixed solution, putting the mixed solution into a hydrothermal reaction kettle to synthesize a carbon precursor in a hydrothermal mode, centrifugally washing the carbon precursor for multiple times by using deionized water, and drying the carbon precursor to obtain the carbon precursor;
in the step, the mass ratio of glucose to ferric nitrate in the mixed solution is 30: 1-30: 6, the concentration of glucose is 10-30 wt%, the hydrothermal synthesis temperature is 140-200 ℃, the hydrothermal synthesis time is 4-16 hours, and the drying temperature is 60-100 ℃;
secondly, carbonizing the carbon precursor obtained in the first step under the protection of nitrogen, and naturally cooling to room temperature to obtain carbon spheres; in the step, the carbonization temperature range is 300-700 ℃ and the carbonization time range is 2-5 hours;
thirdly, weighing ferric nitrate according to a certain iron-carbon ratio, dissolving the ferric nitrate with 50ml of deionized water to prepare a solution, taking 50g of the carbon spheres obtained in the second step, and slowly adding 50g of the carbon spheres into the solution prepared in the step under stirring; soaking for a certain time after uniformly stirring, and then drying; finally, roasting in a muffle furnace, and naturally cooling to room temperature to obtain a catalyst;
the range of the certain iron-carbon ratio in the step is 3: 50-9: 50; the dipping time ranges from 6 hours to 24 hours; the roasting temperature is 300-500 deg.c and the roasting time is 2-5 hr.
2. The method for preparing the catalyst for molten salt electrochemical synthesis of ammonia according to claim 1, wherein the method comprises the following steps: in the first step, the mass ratio of glucose to ferric nitrate in the mixed solution is 30:3, the glucose concentration is 23 wt%, the hydrothermal synthesis temperature is 180 ℃, and the hydrothermal synthesis time is 8 hours; in the second step, the carbonization temperature is 500 ℃ and the carbonization time is 3 hours; in the third step, the iron-carbon ratio is 7:50, the impregnation time is 24 hours, the roasting temperature is 300 ℃, and the roasting time is 3 hours.
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