CN116062785B - Ruthenium doped lanthanum sulfide catalyst and preparation and application thereof - Google Patents
Ruthenium doped lanthanum sulfide catalyst and preparation and application thereof Download PDFInfo
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- CN116062785B CN116062785B CN202310230252.2A CN202310230252A CN116062785B CN 116062785 B CN116062785 B CN 116062785B CN 202310230252 A CN202310230252 A CN 202310230252A CN 116062785 B CN116062785 B CN 116062785B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YTYSNXOWNOTGMY-UHFFFAOYSA-N lanthanum(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[La+3].[La+3] YTYSNXOWNOTGMY-UHFFFAOYSA-N 0.000 title claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 39
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 239000002073 nanorod Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 229910009111 xH2 O Inorganic materials 0.000 claims description 3
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002055 nanoplate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017586 La2S3 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/288—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The invention discloses a ruthenium doped lanthanum sulfide catalyst, a preparation method thereof and application thereof in electrocatalytic ammonia synthesis, and belongs to the technical field of electrocatalytic materials. The La 2S3 nano rod is obtained through hydrothermal reaction; and then mixing the ruthenium precursor with the La 2S3 nano rod for secondary hydrothermal reaction to obtain the Ru/La 2S3 catalyst. The ruthenium doped lanthanum sulfide electrocatalytic material is synthesized through simple hydrothermal synthesis, the preparation raw materials are cheap and easy to obtain, the method does not contain heavy metals polluting the environment, can realize high-efficiency synthesis of ammonia under the electrocatalytic condition, and has important application prospects.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic materials, and particularly relates to a ruthenium doped lanthanum sulfide catalyst, and preparation and application thereof in electrocatalytic ammonia synthesis.
Background
Electrochemical catalysis has been a hot spot in research in the technical field of clean energy because of the advantages of simple operation, high energy conversion rate, environmental friendliness, sustainable green development and the like. N 2 molecules are converted into a high added value product NH 3 through an electrochemical catalysis method to realize high-efficiency conversion of energy, and the method is an effective method for reducing N 2 to convert the NH 3/NH4 +. In addition, the electric energy is introduced into the synthetic ammonia reaction, and the method has the advantages that the nitrogen molecules are activated in an auxiliary manner in the process of introducing the electric energy into the synthetic ammonia, the thermodynamic limit is broken, the normal-temperature and normal-pressure electrochemical synthesis of ammonia can be realized, renewable green and environment-friendly hydrogen such as rich water on the earth can be used as a raw material, and the dependence of the synthetic ammonia on non-renewable resources is avoided. Therefore, the electrochemical synthesis of ammonia is one of various ammonia synthesis technologies which have more researches and relatively mature mechanisms, is expected to replace the traditional Haber-Bosch ammonia synthesis technology, and has great development prospect and application prospect.
At present, the electrocatalytic synthesis ammonia catalyst is mainly transition metal oxide, but has low ammonia yield and Faraday efficiency, and can not be industrialized far. The metal sulfide has high ammonia yield but poor stability, and thus modification is required to improve stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a ruthenium doped lanthanum sulfide catalyst, a preparation method thereof and application thereof in electrocatalytic synthesis of ammonia, wherein the raw materials are cheap and easy to obtain, the preparation method is simple and convenient, and no environmental pollution substances are involved in the preparation process.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A ruthenium doped lanthanum sulfide catalyst is prepared by hydrothermal method to prepare La 2S3 nanometer rod; then dispersing the ruthenium precursor and the La 2S3 nano rod in water together, and obtaining the Ru/La 2S3 catalyst through secondary hydrothermal reaction.
The preparation of the Ru/La 2S3 catalyst comprises the following steps:
1) Dissolving a certain amount of La (NO 3)3·6H2 O and Na 2S·9H2 O in deionized water respectively, and fully stirring and mixing to prepare a mixed solution;
2) Cooling the obtained mixed solution after hydrothermal reaction, and filtering and washing;
3) Vacuum drying the obtained precipitate to obtain La 2S3 nano rod;
4) Weighing a certain amount of ruthenium precursor and the La 2S3 nano rod obtained in the step 3), and dispersing the ruthenium precursor and the La 2S3 nano rod in water by ultrasonic treatment;
5) Magnetically stirring the mixed solution obtained in the step 4) at room temperature to form uniform suspension;
6) And 5) carrying out secondary hydrothermal reaction on the suspension obtained in the step 5) to obtain the Ru/La 2S3 catalyst.
Further, in step 1), la (molar ratio of NO 3)3·6H2 O to Na 2S·9H2 O was 1:1.
Further, the temperature of the hydrothermal reaction in the step 2) is 150 ℃ and the time is 12 hours.
Further, the temperature of the vacuum drying in the step 3) is 50 ℃ and the time is 24 h.
Further, the molar ratio of ruthenium precursor to La 2S3 nanorods used in step 4) was 1:20. The ruthenium precursor is RuCl 3·xH2 O.
Further, the magnetic stirring time in the step 5) is 1 h.
Further, the temperature of the secondary hydrothermal reaction in the step 6) is 150 ℃ and the time is 12 h.
The obtained ruthenium doped lanthanum sulfide can be used for electrocatalytic synthesis of ammonia. The reaction mechanism of electrocatalytic synthesis of ammonia may be a combined remote mechanism: at the end of the catalyst surface, an N 2 molecule is adsorbed, then the nitrogen atom furthest from the catalyst surface reacts first, and three protons combine with it in turn to form an NH 3 molecule, and the other nitrogen atom is then hydrogenated to form a second NH 3 molecule (see fig. 1).
Compared with the prior art, the invention has the beneficial effects that:
The preparation conditions of the invention are simple and convenient, the preparation is mainly realized by hydrothermal method, and the preparation process does not involve substances polluting the environment, so that the raw materials are easy to obtain. The catalyst is applied to electrocatalytic synthesis of ammonia for the first time, shows excellent ammonia yield (the ammonia yield is 19.40 mu g h −1mg−1 cat), has good stability, and has development significance for the application of the subsequent materials in electrocatalytic synthesis of ammonia.
Drawings
FIG. 1 shows the reaction mechanism of the Ru/La 2S3 catalyst of the present invention for electrocatalytic synthesis of ammonia.
FIG. 2 is an XRD pattern of the Ru/La 2S3 catalyst prepared in the example.
FIG. 3 is an SEM spectrum of a Ru/La 2S3 catalyst prepared according to the example.
FIG. 4 is a TEM photograph of the Ru/La 2S3 catalyst prepared in the example.
FIG. 5 is an XPS photograph of the Ru/La 2S3 catalyst prepared in the examples.
FIG. 6 is a schematic diagram of an apparatus for performing electrocatalytic synthesis of ammonia.
FIG. 7 is a graph comparing ammonia production effects of Ru/La 2S3 catalysts prepared with different doping amounts (doping molar amounts of 0.3%, 0.4%, 0.5%, 1.0%, 2.5% and 5.0%) of the ruthenium precursor.
FIG. 8 is a graph showing the ammonia production effect of the Ru/La 2S3 catalyst prepared in the example.
FIG. 9 is a graph showing comparison of the ammonia production effects of Ru/La 2O3 (a) and Ru/La 2S3 (b).
FIG. 10 shows cyclic voltammograms of Ru/La 2O3 (a) versus Ru/La 2S3 (b) and electrochemical surface areas (c) for both.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Examples
0.3 Mol lanthanum nitrate and 0.3 mol sodium sulfide were dissolved in 40 mL deionized water, respectively, and stirred on a magnetic stirrer to form a uniform solution. Then adding sodium sulfide solution into lanthanum nitrate solution, and magnetically stirring to form uniform suspension. And pouring the suspension into a polytetrafluoroethylene lining (100 mL), placing the suspension into a hydrothermal kettle, and placing the hydrothermal kettle in an electric furnace at 150 ℃ for 12 hours to realize hydrothermal reaction. After the reaction is completed, cooling at room temperature, centrifugating 3500 rpm, washing the obtained precipitate with deionized water, and drying 24: 24h at 50 ℃ to obtain La 2S3 nano-rod.
1G of the prepared La 2S3 nano rod and 0.0276g of RuCl 3·xH2 O (the molar ratio is 20:1) are weighed, placed in a beaker, added with deionized water, subjected to ultrasonic treatment for 30min, and magnetically stirred for 1h to form a uniform solution; transferring the solution into a hydrothermal kettle, performing secondary hydrothermal reaction at 150 ℃ for 12 h, alternately washing and filtering the obtained precipitate with deionized water and absolute ethyl alcohol for six times, and performing vacuum drying at 50 ℃ for 24 hours to obtain the Ru/La 2S3 material with the doping mole amount of 0.5%.
FIG. 2 is an XRD pattern of the resulting Ru/La 2S3 catalyst. As can be seen from the figure, the synthesized Ru/La 2S3 has a high crystallinity, and its XRD pattern is completely identical to that of the standard card (01-089-4035).
FIG. 3 is an SEM image of the resulting Ru/La 2S3 catalyst. As can be seen from the figure, the morphology is nanorods and nanoplates.
FIG. 4 is a TEM image (a, b) and an HRTEM image (c, d) of the obtained Ru/La 2S3 catalyst. The prepared catalyst was further verified in the TEM image to retain the original nanorod morphology of lanthanum sulfide. Meanwhile, the HRTEM diagram proves that obvious lattice fringes exist, the distance between adjacent fringes is 0.332 nm, and the (220) crystal face corresponds to the adjacent fringes. The high angle annular dark field scanning transmission electron microscope (HAADF-STEM) can further illustrate the nano structure of Ru/La 2S3.
The surface electron properties of the obtained Ru/La 2S3 catalyst were analyzed by XPS technique, and the results are shown in FIG. 5. FIG. 5 demonstrates the presence of La, ru and S elements.
The activity of the prepared Ru/La 2S3 catalyst for electrocatalytic synthesis of ammonia was tested by using a reaction apparatus as shown in FIG. 6, and the operation steps thereof were as follows: the catalyst ink was prepared by dispersing 10 mg Ru/La 2S3 and 50. Mu.L of Nafion solution (5 wt%) in a mixed solution of 475. Mu.L of ethanol and 475. Mu.L of water. Then 10 μl was coated on 1×1 cm 2 Carbonized Paper (CP) and dried under ambient conditions.
All electrochemical measurements were made using the Chenhua CHI660E workstation. NRR electrochemical measurements were performed in H-type cells separated by Nafion membranes and filled with 0.1M Na 2SO4 solution, a typical three-electrode system comprising a platinum electrode as the counter electrode, ag/AgCl as the reference electrode and Ru/La 2S3 nano-plate loaded carbon paper as the working electrode (Ru/La 2S3/CP;Ru/La2S3 nano-plate loading: 0.1 mg). During testing, the working electrode is firstly placed in 0.1M Na 2SO4 electrolyte to be saturated with nitrogen for 30: 30 min; pure nitrogen was then bubbled into the electrolyte for continuous injection in a two hour reaction, and the catalytic performance of NRR was tested at a controlled applied voltage. All potentials are converted to RHE units. All measurements were performed at room temperature (25 ℃). Meanwhile, in order to verify the stability of the catalyst, eight repeated experiments were performed under the same conditions.
FIG. 7 is a graph comparing ammonia production effects of Ru/La 2S3 catalysts prepared with different doping amounts (doping molar amounts of 0.3%, 0.4%, 0.5%, 1.0%, 2.5% and 5.0%) of the ruthenium precursor. As can be seen from the graph, the activity was optimal at a Ru/La 2S3 molar ratio of 1:20, and the ammonia yield was 19.7. Mu. g h -1mg-1 cat.
FIG. 8 is a graph showing the ammonia production effect of the Ru/La 2S3 catalyst prepared in the example, wherein a is an ammonia yield graph and b is a stability test graph. As can be seen from the graph, the ammonia yield is negligible under the conditions of no catalyst drop, ar atmosphere and open circuit voltage, and the ammonia yield of the Ru/La 2S3 catalyst is improved by two times (a) compared with that of the La 2S3 catalyst; while the ammonia yield of the eight repeated experiments under the same conditions remained almost unchanged, it was found that the catalyst had excellent stability (b).
Comparative example
0.75 G La (CH 3COO)3H2 O is dissolved in 30mL of water, 0.42 g K 2CO3 is dissolved in 30mL of ethanol to form two transparent solutions respectively, then the two solutions are fully stirred and mixed at room temperature, the hydrothermal reaction is carried out at 180 ℃ for 24 h, the obtained mixed solution is cooled, filtered and washed, dried at 80 ℃, the obtained precipitate is calcined at 690 ℃ under Ar atmosphere for 6 h to obtain La 2O3, the ruthenium precursor and La 2O3 are mixed according to the molar ratio of 1:20, the hydrothermal reaction is carried out at 180 ℃ for 24 h, and the Ru/La 2O3 catalyst is obtained after the filtration and washing and the drying at 80 ℃.
FIG. 9 is a graph showing the comparison of the ammonia production effect of the Ru/La 2O3 catalyst (a) and the Ru/La 2S3 catalyst (b). As shown, the ammonia yield of the reversible hydrogen electrode of Ru/La 2O3 at-0.6V was up to 10.7 μ g h -1mg-1 cat, while the optimal ammonia yield of Ru/La 2S3 was 19.4 μ g h -1mg-1 cat, doubling the ammonia yield relative to Ru/La 2O3 and decreasing the Faraday efficiency by a factor of two.
To further compare the difference in Ru/La 2S3 and Ru/La 2O3 activities, cyclic voltammetry tests were performed in the non-Faraday region at different scan rates, the results are shown in FIG. 10. As can be seen from the graph, the electrochemical active area of Ru/La 2S3 is twice that of Ru/La 2O3, the active area is increased, and the active sites are increased, so that the yield of ammonia generated by nitrogen adsorption and activation is higher.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (4)
1. A preparation method of a ruthenium doped lanthanum sulfide catalyst is characterized in that La 2S3 nano rods are prepared by hydrothermal method; then dispersing the ruthenium precursor and the La 2S3 nano rod in water together, and preparing the Ru/La 2S3 catalyst through secondary hydrothermal reaction;
the preparation of the La 2S3 nano rod comprises the following steps:
1) Respectively dissolving La (NO 3)3·6H2 O and Na 2S·9H2 O in deionized water, and fully stirring and mixing to prepare a mixed solution;
2) Cooling the obtained mixed solution after hydrothermal reaction, and filtering and washing;
3) Vacuum drying the obtained precipitate to obtain the La 2S3 nano rod;
la (molar ratio of NO 3)3·6H2 O to Na 2S·9H2 O was 1:1 in step 1);
the temperature of the hydrothermal reaction in the step 2) is 150 ℃ and the time is 12 hours;
The molar ratio of the ruthenium precursor to the La 2S3 nano rod is 1:20; the ruthenium precursor is RuCl 3·xH2 O;
The temperature of the secondary water heating is 150 ℃ and the time is 12 h.
2. The method for preparing a ruthenium doped lanthanum sulfide catalyst according to claim 1, wherein the temperature of the vacuum drying in the step 3) is 50 ℃ and the time is 24h.
3.A ruthenium doped lanthanum sulphide catalyst obtainable by the process of claim 1.
4. Use of ruthenium-doped lanthanum sulphide according to claim 3 for electrocatalytic synthesis of ammonia.
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