CN114990569B - Electrocatalytic deuterium analysis material of boron carbide loaded ruthenium and preparation method and application thereof - Google Patents
Electrocatalytic deuterium analysis material of boron carbide loaded ruthenium and preparation method and application thereof Download PDFInfo
- Publication number
- CN114990569B CN114990569B CN202210537464.0A CN202210537464A CN114990569B CN 114990569 B CN114990569 B CN 114990569B CN 202210537464 A CN202210537464 A CN 202210537464A CN 114990569 B CN114990569 B CN 114990569B
- Authority
- CN
- China
- Prior art keywords
- boron carbide
- ruthenium
- deuterium
- electrocatalytic
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 73
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 39
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 title claims description 31
- 229910052805 deuterium Inorganic materials 0.000 title claims description 31
- 238000004458 analytical method Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000003303 ruthenium Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920000557 Nafion® Polymers 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 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 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 230000008569 process Effects 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
- 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
- 239000000843 powder 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
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 2
- 238000007603 infrared drying Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910052722 tritium Inorganic materials 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 16
- 239000010411 electrocatalyst Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000010494 dissociation reaction Methods 0.000 abstract 1
- 230000005593 dissociations Effects 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- -1 alkali metal deuterium oxide Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000009206 nuclear medicine Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
-
- 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
- C25B11/073—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the field of electrocatalytic materials, and discloses an electrocatalytic deuterium-separating material of boron carbide loaded ruthenium, and a preparation method and application thereof. The material is mainly a boron carbide deuterium-separating electrocatalyst loaded with Ru nanoclusters. Specifically, ru precursor is loaded on boron carbide by wet chemical impregnation method, and finally H is used for preparing the boron carbide 2 The deuterium-separating electrocatalyst is obtained by a reduction method. The invention has the advantages that the boron carbide carrier which is resistant to chemical corrosion, high-temperature oxidation and high in hardness is used, and the capability of the catalyst for water dissociation is improved by utilizing the synergistic effect between ruthenium and boron carbide. The catalyst of the invention has better performance than commercial Pt/C under alkaline condition, can maintain long-time stability under high current density, has the production cost of only 10% of commercial Pt/C catalyst, has strong economic applicability and simple preparation, and is suitable for large-scale application in industry.
Description
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to an electrocatalytic deuterium-separating material of boron carbide loaded ruthenium, and a preparation method and application thereof.
Background
Deuterium is also known as deuterium, symbol D or 2 H, an isotope of hydrogen. Deuterium content in the hydrogen is 0.02%. Most of physical and chemical properties of deuterium are similar to hydrogen, and deuterium is a colorless, odorless, nontoxic and harmless combustible gas at normal temperature. The method is used for nuclear energy, controllable nuclear fusion reaction, deuterated optical fibers, deuterium lubricating oil, lasers, bulbs, experimental research, semiconductor material toughening treatment, nuclear medicine, nuclear agriculture and other aspects; in addition, it has some important uses in military, such as the manufacture of hydrogen ammunition, middle ammunition and eastern wind laser weapons.
The main preparation methods of deuterium include liquid hydrogen rectification, electrolytic heavy water, palladium/alloy film or metal hydride method. The electrolytic heavy water method is to electrolyze deuterium mainly by using a catalyst with lower overpotential as a cathode, deuterium water as electrolyte and deuterium oxide of alkali metal as electrolyte through an electrolysis device. The method is simple and efficient, has low equipment requirement, and has high purity of the prepared deuterium gas, so that the method is of great concern.
The overpotential and material stability of the electrolytic heavy water cathode catalyst have been the focus of research, and in terms of overpotential, noble metal platinum (Pt) is considered to be the optimal electrolytic water material due to its lower overpotential, but the scarcity and expensive price of Pt catalysts limit the wide application of Pt, so development of a catalyst for replacing Pt is urgent. Ruthenium (Ru) is a much cheaper noble metal, the cost of which is only about one sixth of that of Pt, and the bond energy strength of Ru and deuterium is comparable to that of Pt. It is therefore important to explore ruthenium-based catalysts with low overpotential.
In terms of material stability, the carrier of a part of the catalyst cannot operate in an acidic or alkaline electrolyte for a long time by electrifying due to the property of the catalyst, otherwise, the catalyst loses catalytic activity due to reasons such as material dissolution or active component separation. The invention uses the boron carbide material with low density, high strength, high temperature stability and good chemical stability, and the boron carbide does not react with acid and alkali solution, and has high chemical level, neutron absorption, wear resistance and semiconductor conductivity. Is one of the most acid stable substances, stable in all concentrated or dilute acid or alkali aqueous solutions, and boron carbide is basically stable in an air environment below 800 ℃.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide the electrocatalytic deuterium-separating material of the boron carbide supported ruthenium, and the preparation method and the application thereof.
The technical scheme provided by the invention is as follows:
the preparation method of the boron carbide supported ruthenium electrocatalytic deuterium separation material comprises the following specific steps:
1) Weighing a certain amount of ruthenium salt as Ru precursor and a certain amount of boron carbide as carrier, adding a certain amount of absolute ethyl alcohol into a beaker, placing into an ultrasonic pool for ultrasonic treatment to enable ruthenium salt in an ethanol solution to be fully dissolved and boron carbide to be uniformly dispersed, adding a magnet after ultrasonic treatment, and placing the beaker into an oil bath pot to be stirred at a certain temperature;
2) After the ethanol in the step 1) is completely volatilized under stirring treatment, taking out the stirred boron carbide powder loaded with ruthenium salt in the beaker, and further drying by using an oven;
3) After the drying reaction of step 2) is completed, the reaction is finished through H 2 Reduction of Ru on boron carbide 3+ The metal Ru is reduced into a metal Ru simple substance, and the specific process is as follows: transferring boron carbide powder to be reduced into a crucible, then placing the crucible into a tube furnace, and heating the crucible at the temperature of 250-450 ℃ under H 2 In atmosphere, through H 2 And Ru (Rust) 3+ Reduction reaction is carried out to lead RuCl 3 Reducing into simple substance Ru. And taking out the material after the calcination is naturally cooled, so as to obtain the electrocatalytic deuterium-separating material of the boron carbide loaded ruthenium.
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, 1) the ultrasonic time in the step is 10-15min, and the temperature of stirring in an oil bath pot is 60-80 ℃; 2) In the step, the drying temperature of the oven is set to be 100-150 ℃.
Further, H in step 3) 2 The specific experimental conditions of the reduction method are as follows: h in calcination 2 The flow rate is 50 mL/min, the heating rate is 5 ℃/min, and the heat preservation time is 3 h.
The invention also discloses an electrocatalytic deuterium-separating material of the boron carbide supported ruthenium prepared by the preparation method.
In addition, the invention also discloses application of the boron carbide supported ruthenium electrocatalytic tritium precipitation material prepared by the preparation method in electrolysis of heavy water.
As a further technical scheme, the electrolysis process is carried out in a single-tank electrolytic cell, a three-electrode electrolytic 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 NaOD heavy water solution with the concentration of 1 mol/L is used as electrolyte to carry out electrochemical deuterium separation reaction.
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, uniformly dispersing the solution by ultrasonic waves, coating the solution on carbon cloth, and finally drying in an infrared drying lamp to obtain a working electrode; the volume ratio of the DuPont nafion solution to the absolute ethyl alcohol is 0.5-2:9, preferably 1:9.
The catalyst prepared by the technology has the following advantages compared with the traditional catalyst:
(1) Compared with the traditional Pt carbon catalyst, ru with the hydrogen bonding capability similar to that of Pt is adopted as an active component, meanwhile, the ruthenium and the boron carbide carrier directly generate a synergistic effect through a hydrogen reduction method, a certain degree of electron transfer occurs between B and Ru on the carrier during high-temperature calcination, ru-B bonds are formed, ru is promoted to be uniformly distributed on the carrier during calcination reduction under the action of B in the boron carbide, and finally Ru nanoclusters are uniformly dispersed on the surface of the boron carbide;
(2) The catalyst adopts boron carbide as a carrier, the boron carbide does not react with acid and alkali solution, has high chemical level, neutron absorption, wear resistance and semiconductor conductivity, is one of the most stable substances for acid, is stable in all concentrated or diluted acid or alkali aqueous solutions and is basically stable below 800 ℃ in an air environment, so the catalyst has high electrocatalytic activity and super-strong stability, and Ru-B bonds on the catalyst obviously reduce the energy barrier of electrolysis heavy water;
(3) Experiments and characterization prove that because Ru is uniformly distributed on the surface of the catalyst carrier in a nano cluster mode, the carrier and metal form good coordination, and TEM discovers that carbon coated Ru metal particles exist at the edge position, the synergistic effect of Ru and the carrier is generated, the conductivity of the catalyst is well enhanced, the active site of the catalyst is increased, the overpotential is reduced, and large current is obtained;
(4) The catalyst disclosed by the invention is completely free of Pt, the noble metal content is far lower than that of a common 20% Pt/C commercial catalyst, and the preparation method of the catalyst is simple, easy to operate, low in cost and environment-friendly, does not need special equipment in the whole preparation process, and is easy for mass production. Is expected to be applied to a large-scale electrolysis heavy water deuterium gas system, replaces the existing technique for preparing deuterium gas by an alkali metal deuterium oxide method, and becomes a source of high added value, green and clean renewable energy.
Drawings
Fig. 1: (a) LSV contrast curves of the boron carbide supported Ru electrocatalysts prepared in examples 1-5 and commercial platinum carbon applied to electrochemical deuterium evolution reactions; (b) The application of the boron carbide supported Ru electrocatalyst prepared for examples 1-5 and commercial platinum carbon to electrochemical deuterium evolution reactions was at 10 mA/cm 2 An over-potential contrast graph at the time;
fig. 2: (a) LSV contrast curves of the boron carbide supported Ru electrocatalysts prepared in examples 6-10 and commercial platinum carbon applied to electrochemical deuterium analysis reactions; (b) The application of the boron carbide supported Ru electrocatalyst prepared for examples 6-10 and commercial platinum carbon to electrochemical deuterium evolution reactions was at 10 mA/cm 2 An over-potential contrast graph at the time;
fig. 3: (a) LSV contrast curves of the boron carbide supported Ru electrocatalysts prepared in examples 11-15 and commercial platinum carbon applied to electrochemical deuterium evolution reactions; (b) The application of the boron carbide supported Ru electrocatalyst prepared for examples 11-15 and commercial platinum carbon to electrochemical deuterium evolution reactions was at 10 mA/cm 2 Over-potential contrast plot at time.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1: the preparation method of the boron carbide supported ruthenium electrocatalytic deuterium separation material (with the loading amount of 1%) comprises the following steps:
accurately weighing 100 mg boron carbide and 2.1 mg ruthenium trichloride in a beaker, weighing 10 g (12.66 mL) absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, taking a magnet, adding the magnet into the beaker, and then placing the magnet in an oil bath pot, heating and stirring at 60 ℃ for 6 h. Pouring the uniformly mixed mixture into a crucible by a spatula, then placing the crucible in a tube furnace, and adding H 2 The temperature is raised from room temperature to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere, and the mixture is calcined at constant temperature for 3 h and then naturally cooled to the room temperature. And taking out the calcined product and grinding uniformly to obtain the boron carbide supported ruthenium electrocatalyst.
Example 2: the preparation method of the electrocatalytic deuterium-separating material (load 3%) of boron carbide loaded ruthenium comprises the following steps:
accurately weighing 100 mg boron carbide and 6.2 mg ruthenium trichloride in a beaker, weighing 10 g (12.66 mL) absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, taking a magnet, adding the magnet into the beaker, and then placing the magnet in an oil bath pot, heating and stirring at 60 ℃ for 6 h. Pouring the uniformly mixed mixture into a crucible by a spatula, then placing the crucible in a tube furnace, and adding H 2 The temperature is raised from room temperature to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere, and the mixture is calcined at constant temperature for 3 h and then naturally cooled to the room temperature. And taking out the calcined product and grinding uniformly to obtain the boron carbide supported ruthenium electrocatalyst.
Example 3: the preparation method of the electrocatalytic deuterium-separating material (load 5%) of boron carbide loaded ruthenium comprises the following steps:
accurately weighing 100 mg boron carbide and 10.3 mg ruthenium trichloride in a beaker, weighing 10 g (12.66 mL) absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, taking a magnet, adding the magnet into the beaker, and then placing the magnet in an oil bath pot, heating and stirring at 60 ℃ for 6 h. Pouring the uniformly mixed mixture into a crucible by a spatula, then placing the crucible in a tube furnace, and adding H 2 The temperature is raised from room temperature to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere, and the mixture is calcined at constant temperature for 3 h and then naturally cooled to the room temperature. And taking out the calcined product and grinding uniformly to obtain the boron carbide supported ruthenium electrocatalyst.
Example 4: the preparation method of the electrocatalytic deuterium-separating material (load of 7%) of boron carbide loaded ruthenium comprises the following steps:
accurately weighing 100 mg boron carbide and 14.4 mg ruthenium trichloride in a beaker, weighing 10 g (12.66 mL) absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, taking a magnet, adding the magnet into the beaker, and then placing the magnet in an oil bath pot, heating and stirring at 60 ℃ for 6 h. Pouring the uniformly mixed mixture into a crucible by a spatula, then placing the crucible in a tube furnace, and adding H 2 The temperature is raised from room temperature to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere, and the mixture is calcined at constant temperature for 3 h and then naturally cooled to the room temperature. And taking out the calcined product and grinding uniformly to obtain the boron carbide supported ruthenium electrocatalyst.
Example 5: the preparation method of the boron carbide supported ruthenium electrocatalytic deuterium separation material (load 10%) comprises the following steps:
accurately weighing 100 mg boron carbide and 20.5 mg ruthenium trichloride in a beaker, weighing 10 g (12.66 mL) absolute ethyl alcohol, adding the absolute ethyl alcohol into the beaker, carrying out ultrasonic treatment for 10 min, taking a magnet, adding the magnet into the beaker, and then placing the magnet in an oil bath pot, heating and stirring at 60 ℃ for 6 h. Pouring the uniformly mixed mixture into a crucible by a spatula, then placing the crucible in a tube furnace, and adding H 2 The temperature is raised from room temperature to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere, and the mixture is calcined at constant temperature for 3 h and then naturally cooled to the room temperature. And taking out the calcined product and grinding uniformly to obtain the boron carbide supported ruthenium electrocatalyst.
The preparation method of the electrocatalytic deuterium-separating material (load capacity of 7%) of the boron carbide loaded ruthenium in the embodiment 6-10 comprises the following steps:
accurately weighing 5 parts of 100 mg boron carbide and 14.4 mg ruthenium trichloride in sequence in 5 beakers, weighing 10 g (12.66 mL) absolute ethyl alcohol, adding the absolute ethyl alcohol into the 5 beakers, carrying out ultrasonic treatment for 10 min, taking the magnetons, respectively adding the magnetons into the beakers, and then placing the beakers into an oil bath pot, heating and stirring at 60 ℃ for 6 h. 5 parts of the mixture were poured into 5 crucibles respectively with a spatula, the crucibles were then placed in a tube furnace, and 5 parts of the mixture were poured into H 2 Calcining at 200 deg.C at a heating rate of 5 deg.C/min under atmosphere(example 6), 250 ℃ (example 7), 300 ℃ (example 8), 350 ℃ (example 9) and 400 ℃ (example 10), and then calcining at constant temperature at different temperatures for 3 h respectively, and naturally cooling to room temperature. And taking out the calcined product and grinding uniformly to obtain the boron carbide supported ruthenium electrocatalyst prepared at different temperatures.
The preparation method of the electrocatalytic deuterium-separating material (load of 7%) of the boron carbide loaded ruthenium in the embodiment 11-15 comprises the following steps:
accurately and sequentially weighing 5 parts of 100 mg boron carbide, 14.4 mg ruthenium trichloride (example 11), 22 mg ruthenium nitrate (example 12), 27.6 mg ruthenium acetylacetonate (example 13), 19.28 mg ruthenium acetate (example 14) and 66.3 mg tris (triphenylphosphine) ruthenium dichloride (example 15) into a beaker, weighing 10 g (12.66 mL) absolute ethyl alcohol into the beaker, adding the magnetons into the 5 beakers respectively after ultrasonic treatment for 10 min, and then placing the beakers into an oil bath pot respectively and heating and stirring the oil bath pot at 60 ℃ for 6 h. 5 parts of the mixture were poured into 5 crucibles respectively with a spatula, the crucibles were then placed in a tube furnace, and 5 parts of the mixture were poured into H 2 The temperature is raised from room temperature to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere, and the mixture is calcined at constant temperature for 3 h and then naturally cooled to the room temperature. And taking out the calcined product and grinding uniformly to obtain the boron carbide supported ruthenium electrocatalyst.
The above-mentioned working electrodes prepared respectively using the catalysts of examples 1 to 15 and commercial platinum carbon catalyst (platinum loading 20 wt%) as raw materials were applied to the test procedure of electrolytic heavy water deuterium-separating reaction: the composite electrode with the catalyst coated on the carbon cloth is used as a working electrode, the graphite rod is used as a counter electrode, and the saturated calomel electrode is used as a reference electrode. The experimental conditions are that the test is carried out in a NaOD heavy water solution with the concentration of 1 mol/L at normal temperature and normal pressure, and the standard voltage range is 0.1 to-0.4V.
Lsv electrochemical Performance graphs and 10 mA/cm for examples 1-5 2 The overpotential comparison chart is shown in fig. 1, and the optimal effect is found by comparison when the Ru loading is 7%, and the characterization analysis shows that the reason is that the active component on the catalyst is too little when the Ru loading is too low, so that deuterium precipitation is caused to be too muchThe potential is higher; and when the loading is too high, the Ru metal particles are found to be aggregated, and the active centers are unevenly dispersed, so that the performance is slightly poor.
Lsv electrochemical Performance graphs and 10 mA/cm for examples 6-10 2 The overpotential comparison chart is shown in fig. 2, and it is found that when the fixed reduction treatment time is 3 h, different reduction temperatures have different effect influences and the effect is optimal at 350 ℃ by comparing the influence of different reduction temperatures on the catalyst. It was found by analysis that the reason is Ru when the reduction temperature is slightly lower 3+ Incomplete reduction results, while too high a temperature may also cause the Ru on the support to agglomerate during reduction, forming large particles and thus causing a decrease in the active sites on the catalyst surface.
Lsv electrochemical Performance graphs and 10 mA/cm for examples 11-15 2 The overpotential comparison is shown in FIG. 3, and it is found that the effect of the different precursors when reduced by hydrogen is different by comparing the catalysts prepared under the same conditions with the ruthenium salts of the different precursors, and H at 300 ℃ is different due to the difference of the ligands in the ruthenium salt compounds 2 RuCl during reduction 3 Is more easily reduced and Cl - The influence on Ru and the carrier is minimal.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (9)
1. The preparation method of the boron carbide supported ruthenium electrocatalytic deuterium separation material is characterized by comprising the following specific steps of:
1) Weighing a certain amount of ruthenium salt as Ru precursor and a certain amount of boron carbide as carrier, adding a certain amount of absolute ethyl alcohol into a beaker, placing into an ultrasonic pool for ultrasonic treatment to enable ruthenium salt in an ethanol solution to be fully dissolved and boron carbide to be uniformly dispersed, adding a magnet after ultrasonic treatment, and placing the beaker into an oil bath pot to be stirred at a certain temperature;
2) After the ethanol in the step 1) is completely volatilized under stirring treatment, taking out the stirred boron carbide powder loaded with ruthenium salt in the beaker, and further drying by using an oven;
3) After the drying reaction of step 2) is completed, the reaction is finished through H 2 Reduction of Ru on boron carbide 3+ The metal Ru is reduced into a metal Ru simple substance, and the specific process is as follows: transferring the boron carbide loaded with ruthenium salt into a crucible, then placing the crucible into a tube furnace, and heating the crucible at the temperature of 300-350 ℃ under H 2 In atmosphere, through H 2 And Ru (Rust) 3+ Taking out the mixture after the reduction reaction is carried out and the calcination is naturally cooled, thereby obtaining the electrocatalytic deuterium-separating material of the boron carbide loaded ruthenium;
the mass ratio of ruthenium to boron carbide in the step 1) is 7% or 10%.
2. The method for preparing the electrocatalytic deuterium-separating material of boron carbide supported ruthenium as claimed in claim 1, wherein the mass ratio of the added amount of absolute ethyl alcohol to the boron carbide in the step 1) is 100:1.
3. The method for preparing the boron carbide supported ruthenium electrocatalytic deuterium deposition material as set forth in claim 1, wherein the ruthenium salt used in the step 1) is one of ruthenium trichloride, ruthenium nitrate, ruthenium acetylacetonate, ruthenium acetate and tris (triphenylphosphine) ruthenium dichloride.
4. The method for preparing the electrocatalytic deuterium-separating material of boron carbide supported ruthenium according to claim 1, wherein the ultrasonic time in the step 1) is 10-15min, and the stirring temperature in an oil bath pot is 60-80 ℃; 2) In the step, the drying temperature of the oven is set to be 100-150 ℃.
5. The method for preparing the electrocatalytic deuterium-separating material of boron carbide supported ruthenium as claimed in claim 1, wherein H in the step 3) is 2 The specific experimental conditions of the reduction method are as follows: h in calcination 2 The flow rate is 50 mL/min, the heating rate is 5 ℃/min, and the heat preservation time is 3 h.
6. An electrocatalytic deuterium deposition material of boron carbide supported ruthenium, characterized in that it is prepared by the preparation method according to any one of claims 1-5.
7. Use of the boron carbide supported ruthenium electrocatalytic tritium analysis material as claimed in claim 6 for electrolysis of heavy water.
8. The application of the electrocatalytic deuterium separation material of boron carbide supported ruthenium according to claim 7, 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 NaOD heavy water solution with the concentration of 1 mol/L is used as electrolyte to carry out electrochemical deuterium separation reaction.
9. The application of the electrocatalytic deuterium-separating material of boron carbide supported ruthenium in electrolysis of heavy water as claimed in claim 8, wherein the preparation method of the working electrode is as follows: adding a catalyst into a mixed solution of a Dupont nafion solution and absolute ethyl alcohol, uniformly dispersing the solution by ultrasonic waves, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537464.0A CN114990569B (en) | 2022-05-18 | 2022-05-18 | Electrocatalytic deuterium analysis material of boron carbide loaded ruthenium and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537464.0A CN114990569B (en) | 2022-05-18 | 2022-05-18 | Electrocatalytic deuterium analysis material of boron carbide loaded ruthenium and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114990569A CN114990569A (en) | 2022-09-02 |
| CN114990569B true CN114990569B (en) | 2023-12-19 |
Family
ID=83028173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210537464.0A Active CN114990569B (en) | 2022-05-18 | 2022-05-18 | Electrocatalytic deuterium analysis material of boron carbide loaded ruthenium and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114990569B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321373A (en) * | 2017-06-15 | 2017-11-07 | 燕山大学 | Doped carbon carrying transition metal boride multifunctional nano catalyst and preparation method |
| CN110743556A (en) * | 2019-09-29 | 2020-02-04 | 浙江工业大学 | Copper-based alloy catalyst and preparation method and application thereof |
| CN111905725A (en) * | 2020-08-25 | 2020-11-10 | 浙江工业大学 | Ru-based catalyst and preparation method and application thereof |
| CN112281176A (en) * | 2020-10-23 | 2021-01-29 | 浙江工业大学 | Nitrogen-doped carbon-coated Ru nano catalyst and application thereof in electrochemical deuterium evolution reaction |
| EP3825443A1 (en) * | 2019-11-22 | 2021-05-26 | Korea Institute of Energy Research | Method of preparing catalyst for pem water electrolysis and catalyst for pem water electrolysis |
| CN113638007A (en) * | 2021-08-26 | 2021-11-12 | 广东电网有限责任公司 | Hydrogen electrolysis catalyst and preparation method thereof |
| CN113684502A (en) * | 2021-09-19 | 2021-11-23 | 华东理工大学 | Preparation method of nitrogen-doped carbon-based supported ruthenium catalyst for hydrogen electrolysis |
| CN114293200A (en) * | 2021-12-15 | 2022-04-08 | 湖南大学 | Porous carbon loaded amorphous/crystalline ruthenium-based high-efficiency hydrogen evolution catalyst and preparation and application thereof |
-
2022
- 2022-05-18 CN CN202210537464.0A patent/CN114990569B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321373A (en) * | 2017-06-15 | 2017-11-07 | 燕山大学 | Doped carbon carrying transition metal boride multifunctional nano catalyst and preparation method |
| CN110743556A (en) * | 2019-09-29 | 2020-02-04 | 浙江工业大学 | Copper-based alloy catalyst and preparation method and application thereof |
| EP3825443A1 (en) * | 2019-11-22 | 2021-05-26 | Korea Institute of Energy Research | Method of preparing catalyst for pem water electrolysis and catalyst for pem water electrolysis |
| CN111905725A (en) * | 2020-08-25 | 2020-11-10 | 浙江工业大学 | Ru-based catalyst and preparation method and application thereof |
| CN112281176A (en) * | 2020-10-23 | 2021-01-29 | 浙江工业大学 | Nitrogen-doped carbon-coated Ru nano catalyst and application thereof in electrochemical deuterium evolution reaction |
| CN113638007A (en) * | 2021-08-26 | 2021-11-12 | 广东电网有限责任公司 | Hydrogen electrolysis catalyst and preparation method thereof |
| CN113684502A (en) * | 2021-09-19 | 2021-11-23 | 华东理工大学 | Preparation method of nitrogen-doped carbon-based supported ruthenium catalyst for hydrogen electrolysis |
| CN114293200A (en) * | 2021-12-15 | 2022-04-08 | 湖南大学 | Porous carbon loaded amorphous/crystalline ruthenium-based high-efficiency hydrogen evolution catalyst and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114990569A (en) | 2022-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN113437314B (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| CN114108004B (en) | Ruthenium-based alloy catalyst and preparation method and application thereof | |
| CN109759066B (en) | Preparation method of boron-doped graphene-loaded cobalt-nickel bimetallic oxide oxygen evolution catalyst | |
| Liu et al. | Synergistic coupling of nickel boride with Ru cluster as a highly active multifunctional electrocatalyst for overall water splitting and glucose electrolysis | |
| CN109621969B (en) | Self-supporting bimetal nickel-tungsten carbide fully-hydrolyzed material and preparation method thereof | |
| CN110560117A (en) | Bimetallic cobalt ruthenium-nitrogen phosphorus doped porous carbon electrocatalyst and preparation method and application thereof | |
| CN104043453B (en) | A kind of support type cobaltosic oxide nano composite catalyst and application | |
| CN114875442A (en) | Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof | |
| CN114990569B (en) | Electrocatalytic deuterium analysis material of boron carbide loaded ruthenium and preparation method and application thereof | |
| CN114196969B (en) | Ruthenium-based oxygen evolution reaction catalyst and preparation method and application thereof | |
| CN112779560B (en) | Preparation method and application of hydrogen evolution catalytic material Pt-CoP | |
| CN111686727B (en) | Preparation method of supported oxygen evolution catalyst and water electrolyzer membrane electrode | |
| CN114561655A (en) | Preparation method and application of rare earth cerium doped nickel sulfide/iron sulfide heterojunction material | |
| CN114717572A (en) | Cobalt-iron bimetal phosphorization nano particle with nitrogen-doped carbon as substrate and preparation method and application thereof | |
| CN115074774B (en) | Rhodium-based hollow porous microsphere/nickel foam electrode and preparation method and application thereof | |
| CN114920302B (en) | Mesoporous multilayer cake-shaped bimetallic oxygen evolution electrocatalyst and preparation method and application thereof | |
| CN116037953B (en) | PtIr alloy nano material and preparation method and application thereof | |
| CN110625136B (en) | Method for efficiently and simply synthesizing Ru nanowire | |
| KR102288276B1 (en) | Preparation method of catalyst for PEM hydrolysis and catalyst for PEM hydrolysis | |
| CN114481160B (en) | Preparation method of CNT-Zn monoatomic catalytic material | |
| CN114774981B (en) | Preparation method and application of ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst | |
| KR102362247B1 (en) | Preparation method of catalyst for PEM hydrolysis and catalyst for PEM hydrolysis | |
| CN114990576A (en) | IrO with load structure 2 Preparation method and application of catalyst | |
| CN115537870A (en) | Boron carbide-based deuterium evolution electrocatalyst prepared by bubble method and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |