CN114990569A - Boron carbide loaded ruthenium electro-catalysis deuterium evolution material and preparation method and application thereof - Google Patents
Boron carbide loaded ruthenium electro-catalysis deuterium evolution material and preparation method and application thereof Download PDFInfo
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- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 72
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 title claims abstract description 49
- 229910052805 deuterium Inorganic materials 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 38
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 title claims description 6
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 26
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- 238000006243 chemical reaction Methods 0.000 claims description 16
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- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
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- 239000000843 powder Substances 0.000 claims description 4
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 4
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 3
- HEMHJVSKTPXQMS-DYCDLGHISA-M Sodium hydroxide-d Chemical compound [Na+].[2H][O-] HEMHJVSKTPXQMS-DYCDLGHISA-M 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 3
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229910052722 tritium Inorganic materials 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 16
- 239000010411 electrocatalyst Substances 0.000 abstract description 15
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
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- 239000000203 mixture Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 7
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
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- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/067—Inorganic compound e.g. ITO, silica or titania
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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Abstract
The invention belongs to the field of electrocatalytic materials, and discloses a boron carbide ruthenium-loaded electrocatalytic deuterium evolution material, and a preparation method and application thereof. The material is mainly a boron carbide deuterium evolution electrocatalyst loaded with Ru nanoclusters. Specifically, a Ru precursor is loaded on boron carbide by a wet chemical impregnation method, and finally H is carried out 2 The deuterium evolution electrocatalyst is prepared by a reduction method. The method has the advantages that the boron carbide carrier which is resistant to chemical corrosion and high-temperature oxidation and has high hardness is used, and the capability of the catalyst for water dissociation is improved by utilizing the synergistic effect of ruthenium and boron carbide. The catalyst of the invention has better performance than commercial Pt/C under alkaline condition, can keep long-time stability under high current density, has the production cost of only 10 percent of that of the commercial Pt/C catalyst, has strong economic applicability and simple preparationAnd is suitable for large-scale industrial application.
Description
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to a boron carbide ruthenium-loaded electrocatalytic deuterium evolution material, and a preparation method and application thereof.
Background
Deuterium also known as deuterium, the symbol D or 2 H, an isotope of hydrogen. The hydrogen gas contains 0.02% of deuterium. Most of the physical and chemical properties of deuterium are similar to those of hydrogen, and at normal temperature, deuterium is colorless, tasteless, nontoxic and harmless combustible gas. The device is used for nuclear energy, controllable nuclear fusion reaction, deuterated optical fiber, deuterated lubricating oil, lasers, bulbs, experimental research, semiconductor material toughening treatment, nuclear medicine, nuclear agriculture and other aspects; in addition, it has important applications in military applications, such as the manufacture of hydrogen bombs, medium bullets and laser weapons from the east wind.
The main preparation methods of deuterium include liquid hydrogen rectification method, electrolytic heavy water method, palladium/alloy film or metal hydride method, etc. The electrolytic deuterium oxide producing process includes electrolyzing electrolytic equipment to produce deuterium with low overpotential catalyst as cathode, deuterium solution as electrolyte and alkali metal deuterium oxide as electrolyte. The method is simple and efficient, has low requirements on equipment, and the prepared deuterium gas has high purity, so that the method is of great interest.
The overpotential and the material stability of the heavy water electrolysis cathode catalyst have been the focus of research, and in the overpotential aspect, the noble metal platinum (Pt) is considered as the best water electrolysis material due to the lower overpotential, but the scarcity and the expensive price of the Pt catalyst limit the wide application of Pt, so that the development of a catalyst for replacing Pt is urgently needed. Ruthenium (Ru) is a much cheaper noble metal, and the cost is only about one sixth of Pt, and the bond energy strength of Ru and deuterium is similar to that of Pt. Therefore, it is very important to search for ruthenium-based catalysts having low overpotentials.
In the aspect of material stability, part of the catalyst carrier cannot work in an acidic or alkaline electrolyte for a long time due to the influence of the property of the catalyst carrier, otherwise the catalyst loses catalytic activity due to the reasons of material dissolution or active component separation and the like. The boron carbide material with low density, high strength, high temperature stability and good chemical stability is used in the invention, and the boron carbide material does not react with acid and alkali solution and has high chemical potential, neutron absorption, wear resistance and semiconductor conductivity. Is one of the most stable substances to acid, is stable in all concentrated or diluted acid or alkali aqueous solutions, and boron carbide is basically stable in an air environment below 800 ℃.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an electrocatalytic deuterium evolution material of boron carbide loaded ruthenium and a preparation method and application thereof.
The technical scheme provided by the invention is as follows:
a preparation method of an electrocatalytic deuterium evolution material of boron carbide loaded ruthenium comprises the following steps:
1) weighing a certain amount of ruthenium salt as a Ru precursor and a certain amount of boron carbide as a carrier in a beaker, adding a certain amount of absolute ethanol into the beaker, placing the beaker in an ultrasonic pool for ultrasonic treatment to fully dissolve the ruthenium salt in the ethanol solution and uniformly disperse the boron carbide, adding a magnet after the ultrasonic treatment, and placing the beaker in an oil bath pot for stirring at a certain temperature;
2) after the ethanol in the step 1) is completely volatilized under stirring treatment, scraping and taking out the stirred and dried boron carbide powder loaded with ruthenium salt in the beaker, and further drying by using an oven;
3) after the drying reaction in step 2) is completed, the reaction is carried out by H 2 Reduction of Ru on boron carbide 3+ Reducing the metal Ru into a simple substance by the following specific process: transferring boron carbide powder to be reduced into a crucible, then placing the crucible into a tube furnace, and carrying out H reaction at the temperature of 250-450 DEG C 2 In the atmosphere, by H 2 And Ru 3+ Reduction reaction is carried out to react RuCl 3 Reducing the solution into elementary substance Ru. And after the calcination is finished and the temperature is naturally reduced, taking out the material to obtain the boron carbide loaded ruthenium electro-catalysis deuterium evolution material.
Further, the mass ratio of the addition amount of the absolute ethyl alcohol to the boron carbide in the step 1) is 100: 1; the mass ratio of the ruthenium salt to the boron carbide is 1-10: 100.
Further, the ruthenium salt used in step 1) is one of ruthenium trichloride, ruthenium nitrate, ruthenium acetylacetonate, ruthenium acetate and tris (triphenylphosphine) ruthenium dichloride.
Further, the ultrasonic time in the step 1) is 10-15min, and the stirring temperature in an oil bath kettle is 60-80 ℃; 2) the drying set temperature of the drying oven in the step is 100-150 ℃.
Further, 3) H in step 2 The reduction method comprises the following specific experimental conditions: h in calcination 2 The flow rate is 50 mL/min, the temperature rise speed is 5 ℃/min, and the heat preservation time is 3 h.
The invention also discloses the boron carbide loaded ruthenium electro-catalysis deuterium evolution material prepared by the preparation method.
In addition, the invention also discloses application of the boron carbide ruthenium-loaded electro-catalytic tritium-separating material prepared by the preparation method in heavy water electrolysis.
As a further technical scheme, the electrolysis process is carried out in a single-groove electrolytic cell, a three-electrode electrolysis system is adopted, a composite electrode prepared by coating the catalyst on carbon cloth is used as a working electrode, a graphite rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and NaOD heavy water solution with the concentration of 1 mol/L is used as electrolyte, so that electrochemical deuterium precipitation reaction is carried out.
As a further technical scheme, the preparation method of the working electrode comprises the following steps: adding a catalyst into a mixed solution of a DuPont nafion solution and absolute ethyl alcohol, dispersing the solution uniformly by using ultrasound, coating the solution on carbon cloth, and finally drying in an infrared drying lamp to obtain a working electrode; wherein the volume ratio of the Dupont nafion solution to the absolute ethyl alcohol is 0.5-2: 9, and preferably 1: 9.
The catalyst prepared by the above technology has the following advantages compared with the traditional catalyst:
(1) compared with the traditional Pt carbon catalyst, the invention adopts Ru with hydrogen bond capacity similar to that of Pt as an active component, and simultaneously leads the ruthenium and the boron carbide carrier to directly generate synergistic action by a hydrogen reduction method, and the B on the carrier and the Ru generate electron transfer to a certain degree during high-temperature calcination to form Ru-B bonds, so that the Ru is promoted to be uniformly distributed on the carrier during calcination and reduction under the action of the B in the boron carbide, and finally the Ru is uniformly dispersed on the surface of the boron carbide in the form of Ru nanoclusters;
(2) because the catalyst selects the boron carbide as a carrier, the boron carbide does not react with acid and alkali solutions, has high chemical potential, neutron absorption, wear resistance and semiconductor conductivity, is one of the most stable substances to acid, is stable in all concentrated or dilute acid or alkali solution, and is basically stable below 800 ℃ in the air environment, the catalyst has high electrocatalytic activity and super-strong stability, and the Ru-B bond on the catalyst obviously reduces the energy barrier of electrolyzing heavy water;
(3) experiments and characterization are combined to verify that the Ru is uniformly distributed on the surface of the catalyst carrier in the form of nanoclusters, the carrier and metal form good coordination, a phenomenon that Ru metal particles are coated by carbon at the edge position is found by TEM, and the Ru and the carrier generate a synergistic effect, so that the conductivity of the catalyst is well enhanced, the active sites of the catalyst are increased, the overpotential is reduced, and the large current is obtained;
(4) the catalyst of the invention does not contain Pt at all, the content of noble metal is far lower than that of the common commercial catalyst of 20 percent Pt/C, the preparation method of the catalyst is simple, the operation is easy, the cost is low, the environment is friendly, the whole preparation process does not need special equipment, and the batch production is easy. Is expected to be applied to the heavy water deuterium gas electrolysis system in a large scale, replaces the existing deuterium gas preparation technology by an alkali metal deuterium oxide method, and becomes a source of clean renewable energy with high added value and green.
Drawings
FIG. 1: (a) the boron carbide-loaded Ru electrocatalyst prepared in the embodiments 1-5 and commercial platinum carbon are applied to an LSV comparison curve of an electrochemical deuterium evolution reaction; (b) boron carbide-loaded Ru electrocatalyst prepared for embodiments 1-5 and commercial platinum carbon applied to electrochemical deuterium evolution reaction at 10 mA/cm 2 Overpotential contrast graph of time;
FIG. 2 is a schematic diagram: (a) for examples 6 to 10The boron carbide supported Ru electrocatalyst and commercial platinum carbon are applied to an LSV comparison curve of an electrochemical deuterium evolution reaction; (b) boron carbide-loaded Ru electrocatalyst prepared for embodiments 6-10 and commercial platinum carbon applied to electrochemical deuterium evolution reaction at 10 mA/cm 2 Overpotential contrast graph of time;
FIG. 3: (a) the boron carbide-loaded Ru electrocatalyst prepared in examples 11-15 and commercial platinum carbon are applied to an LSV comparison curve of an electrochemical deuterium evolution reaction; (b) the boron carbide-loaded Ru electrocatalyst prepared in examples 11-15 and commercial platinum carbon are applied to an electrochemical deuterium evolution reaction at 10 mA/cm 2 Overpotential versus time plot.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1: the preparation method of the boron carbide ruthenium-loaded electro-catalytic deuterium evolution material (loading amount is 1%) comprises the following steps:
accurately weighing 100 mg of boron carbide and 2.1 mg of ruthenium trichloride in a beaker, weighing 10 g (12.66 mL) of absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, adding a magneton into the beaker, and then placing the beaker in an oil bath kettle to heat and stir at 60 ℃ for 6 h. Pouring the homogeneously mixed mixture into a crucible using a spatula, subsequently placing the crucible in a tube furnace in H 2 Raising the temperature from room temperature to 300 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere, calcining at the constant temperature for 3 h, and naturally cooling to the room temperature. And taking out the calcined product and uniformly grinding to obtain the boron carbide supported ruthenium electrocatalyst.
Example 2: the preparation method of the boron carbide ruthenium-loaded electro-catalytic deuterium evolution material (the load is 3%) comprises the following steps:
accurately weighing 100 mg of boron carbide and 6.2 mg of ruthenium trichloride in a beaker, weighing 10 g (12.66 mL) of absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, adding a magneton into the beaker, and then placing the beaker in an oil bath kettle to heat and stir at 60 ℃ for 6 h. Pouring the homogeneously mixed mixture into a crucible using a spatula, subsequently placing the crucible in a tube furnace in H 2 Raising the temperature from room temperature to 300 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere, calcining at the constant temperature for 3 h, and naturally cooling to the room temperature. And taking out the calcined product and uniformly grinding to obtain the boron carbide supported ruthenium electrocatalyst.
Example 3: the preparation method of the boron carbide supported ruthenium electro-catalysis deuterium evolution material (with the supported amount of 5%) comprises the following steps:
accurately weighing 100 mg of boron carbide and 10.3 mg of ruthenium trichloride in a beaker, weighing 10 g (12.66 mL) of absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, adding a magneton into the beaker, and then placing the beaker in an oil bath kettle to heat and stir at 60 ℃ for 6 h. Pouring the homogeneously mixed mixture into a crucible using a spatula, subsequently placing the crucible in a tube furnace in H 2 Raising the temperature from room temperature to 300 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere, calcining at the constant temperature for 3 h, and naturally cooling to the room temperature. And taking out the calcined product and uniformly grinding to obtain the boron carbide supported ruthenium electrocatalyst.
Example 4: the preparation method of the boron carbide ruthenium-loaded electro-catalytic deuterium evolution material (load is 7%) comprises the following steps:
accurately weighing 100 mg of boron carbide and 14.4 mg of ruthenium trichloride in a beaker, then weighing 10 g (12.66 mL) of absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, then adding a magneton into the beaker, and then placing the beaker in an oil bath kettle to heat and stir at 60 ℃ for 6 h. Pour the homogeneously mixed mixture into a crucible with a spatula, then place the crucible in a tube furnace in H 2 Raising the temperature from room temperature to 300 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere, calcining at the constant temperature for 3 h, and naturally cooling to the room temperature. And taking out the calcined product and uniformly grinding to obtain the boron carbide supported ruthenium electrocatalyst.
Example 5: the preparation method of the boron carbide ruthenium-loaded electro-catalytic deuterium evolution material (loading amount is 10%) comprises the following steps:
accurately weighing 100 mg of boron carbide and 20.5 mg of ruthenium trichloride in a beaker, weighing 10 g (12.66 mL) of absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, adding a magneton into the beaker, and then placing the beaker in an oil bath kettle to heat and stir at 60 ℃ for 6 h. Administration of drugsThe homogeneously mixed mixture was poured into a crucible by scraping, and the crucible was subsequently placed in a tube furnace in H 2 Raising the temperature from room temperature to 300 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere, calcining at the constant temperature for 3 h, and naturally cooling to the room temperature. And taking out the calcined product and uniformly grinding to obtain the boron carbide supported ruthenium electrocatalyst.
Example 6-10 a method for preparing a boron carbide ruthenium-supported electrocatalytic deuterium evolution material (load amount 7%) as follows:
accurately weighing 5 parts of 100 mg boron carbide and 14.4 mg ruthenium trichloride in 5 beakers in sequence, weighing 10 g (12.66 mL) of absolute ethyl alcohol, adding the absolute ethyl alcohol into the 5 beakers, carrying out ultrasonic treatment for 10 min, respectively adding magnetons into the beakers, and then placing the beakers into an oil bath kettle to be heated and stirred for 6 h at the temperature of 60 ℃. Pouring 5 parts of the mixture into 5 crucibles, respectively, using a spatula, placing the crucibles in a tube furnace, and adding 5 parts of the mixture to H 2 Calcining at a temperature increasing rate of 5 ℃/min under the atmosphere for 200 ℃ (example 6), 250 ℃ (example 7), 300 ℃ (example 8), 350 ℃ (example 9) and 400 ℃ (example 10), calcining at different temperatures for 3 h, and naturally cooling to room temperature. And taking out the calcined product and uniformly grinding to obtain the boron carbide supported ruthenium electrocatalyst prepared at different temperatures.
Example 11-15 a method for preparing a boron carbide ruthenium-supported electrocatalytic deuterium evolution material (loading amount 7%) is as follows:
accurately weighing 5 parts of 100 mg of boron carbide, 14.4 mg of ruthenium trichloride (example 11), 22 mg of ruthenium nitrate (example 12), 27.6 mg of ruthenium acetylacetonate (example 13), 19.28 mg of ruthenium acetate (example 14) and 66.3 mg of tris (triphenylphosphine) ruthenium dichloride (example 15) in turn in a beaker, weighing 10 g (12.66 mL) of absolute ethanol, adding the absolute ethanol into the beaker, carrying out ultrasonic treatment for 10 min, taking magnetons, respectively adding the magnetons into 5 beakers, and respectively placing the beakers in an oil bath kettle to be heated and stirred at 60 ℃ for 6 h. Pouring 5 parts of the mixture into 5 crucibles, respectively, using a spatula, placing the crucibles in a tube furnace, and adding 5 parts of the mixture to H 2 Heating from room temperature to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere, and then keeping the temperature constantAnd (4) carrying out warm calcination for 3 h, and then naturally cooling to room temperature. And taking out the calcined product and uniformly grinding to obtain the boron carbide supported ruthenium electrocatalyst.
The working electrodes prepared from the catalysts of examples 1 to 15 and commercial platinum-carbon catalysts (platinum loading 20 wt%) were used in the testing process of electrolytic deuterium desorption reaction: and a composite electrode with a catalyst coated on carbon cloth is used as a working electrode, a graphite rod is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. The test is carried out in 1 mol/L NaOD heavy water solution at normal temperature and normal pressure, and the standard voltage range is 0.1 to-0.4V.
Lsv electrochemical performance diagrams and 10 mA/cm of examples 1 to 5 2 The overpotential comparison graph is shown in fig. 1, the comparison shows that the effect is best when the loading amount of Ru is 7%, and the characterization analysis shows that the overpotential of deuterium evolution is higher because the active component on the catalyst is too little when the loading amount of Ru is too low; when the amount of the supported Ru metal particles is too high, aggregation of Ru metal particles is observed, and the active sites are not uniformly dispersed, resulting in slightly poor performance.
Lsv electrochemical performance diagrams and 10 mA/cm of examples 6 to 10 2 The overpotential comparison graph is shown in fig. 2, and the effect of different reduction temperatures on the catalyst is shown by comparing the effects of different reduction temperatures, and the effect is best at 350 ℃ when the fixed reduction treatment time is 3 hours. It was found by analysis that this is because Ru is present at a slightly lower reduction temperature 3+ The reduction is not complete, and too high a temperature can cause the Ru on the carrier to agglomerate during reduction, forming large particles and reducing the active centers on the surface of the catalyst.
Lsv electrochemical Performance plots and 10 mA/cm for examples 11-15 2 Overpotential comparison of time as shown in FIG. 3, it was found by comparing catalysts prepared under the same conditions with different precursors of ruthenium salt that the different precursors have different effects when reduced by hydrogen, due to the difference of ligands in the ruthenium salt compound, H at 300 deg.C 2 RuCl in reduction 3 Is more easily reduced, and Cl - The influence between Ru and a carrier is minimal.
The description is given for the sole purpose of illustrating the invention concept in its implementation form and the scope of the invention should not be considered as being limited to the particular form set forth in the examples.
Claims (10)
1. A preparation method of an electrocatalytic deuterium evolution material of boron carbide loaded ruthenium is characterized by comprising the following steps:
1) weighing a certain amount of ruthenium salt as a Ru precursor and a certain amount of boron carbide as a carrier in a beaker, adding a certain amount of absolute ethanol into the beaker, placing the beaker in an ultrasonic pool for ultrasonic treatment to fully dissolve the ruthenium salt in the ethanol solution and uniformly disperse the boron carbide, adding a magnet after the ultrasonic treatment, and placing the beaker in an oil bath pot for stirring at a certain temperature;
2) after the ethanol in the step 1) is completely volatilized under stirring treatment, scraping and taking out the stirred and dried boron carbide powder loaded with ruthenium salt in the beaker, and further drying by using an oven;
3) after the drying reaction in step 2) is completed, the reaction is carried out by H 2 Reduction of Ru on boron carbide 3+ Reducing the metal Ru into a simple substance by the following specific process: transferring boron carbide powder to be reduced into a crucible, then placing the crucible into a tube furnace, and carrying out H reaction at the temperature of 250-450 DEG C 2 In the atmosphere, by H 2 And Ru 3+ Reduction reaction is carried out to react RuCl 3 Reducing the ruthenium into elementary substance Ru, and taking out the elementary substance Ru after the calcination is finished and the temperature is naturally reduced, thereby obtaining the boron carbide loaded ruthenium electro-catalysis deuterium evolution material.
2. The method for preparing the boron carbide ruthenium-supported electro-catalytic deuterium evolution material according to claim 1, wherein the mass ratio of the addition amount of the absolute ethyl alcohol to the boron carbide in the step 1) is 100: 1.
3. The preparation method of the boron carbide ruthenium-supported electro-catalytic deuterium evolution material according to claim 1, wherein the mass ratio of ruthenium salt to boron carbide in the step 1) is 1-10: 100.
4. The method for preparing the electrocatalytic deuterium evolution material of boron carbide-supported ruthenium according to claim 1, wherein the ruthenium salt used in the step 1) is one of ruthenium trichloride, ruthenium nitrate, ruthenium acetylacetonate, ruthenium acetate and ruthenium tris (triphenylphosphine) dichloride.
5. The preparation method of the electrocatalytic deuterium evolution material of boron carbide loaded ruthenium according to claim 1, wherein in the step 1), the ultrasonic time is 10-15min, and the stirring temperature in an oil bath is 60-80 ℃; 2) in the step, the drying set temperature of the drying oven is 100-150 ℃.
6. The method for preparing the electrocatalytic deuterium evolution material of boron carbide loaded ruthenium according to claim 1, wherein H in the step 3) is 2 The reduction method comprises the following specific experimental conditions: h in calcination 2 The flow rate is 50 mL/min, the temperature rise speed is 5 ℃/min, and the heat preservation time is 3 h.
7. A boron carbide supported ruthenium electrocatalytic deuterium evolution material prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the boron carbide supported ruthenium electrocatalytic tritium precipitation material of claim 7 in electrolysis of heavy water.
9. The application of the boron carbide ruthenium-supported electro-catalytic deuterium evolution material in heavy water electrolysis according to claim 8, wherein the electrolysis process is carried out in a single-tank electrolytic cell, a three-electrode electrolysis system is adopted, a composite electrode prepared by coating the catalyst on carbon cloth is used as a working electrode, a graphite rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and a 1 mol/L concentration NaOD heavy water solution is used as an electrolyte, so that the electrochemical deuterium evolution reaction is carried out.
10. The use of the boron carbide supported ruthenium electrocatalytic deuterium evolution material of claim 9 in the electrolysis of heavy water, characterized in that the working electrode is prepared by the following method: adding a catalyst into a mixed solution of a DuPont nafion solution and absolute ethyl alcohol, dispersing the solution uniformly by using ultrasound, coating the solution on carbon cloth, and finally drying in an infrared drying lamp to obtain a working electrode; wherein the volume ratio of the Dupont nafion solution to the absolute ethyl alcohol is 0.5-2: 9, and preferably 1: 9.
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