CN114774981B - Preparation method and application of ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst - Google Patents
Preparation method and application of ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst Download PDFInfo
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- CN114774981B CN114774981B CN202210537468.9A CN202210537468A CN114774981B CN 114774981 B CN114774981 B CN 114774981B CN 202210537468 A CN202210537468 A CN 202210537468A CN 114774981 B CN114774981 B CN 114774981B
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 33
- 238000000227 grinding Methods 0.000 claims abstract description 26
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 24
- 238000004108 freeze drying Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 12
- 239000005011 phenolic resin Substances 0.000 claims abstract description 12
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000197 pyrolysis Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 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
- SUCQPHMWFOCTTR-UHFFFAOYSA-L dichlororuthenium;triphenylphosphane Chemical compound Cl[Ru]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SUCQPHMWFOCTTR-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
- 238000001035 drying Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 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 3
- 238000007603 infrared drying Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 5
- 239000010411 electrocatalyst Substances 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003776 cleavage reaction Methods 0.000 abstract 1
- 230000007017 scission Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 18
- 229910052805 deuterium Inorganic materials 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 238000011068 loading method Methods 0.000 description 5
- 238000007790 scraping Methods 0.000 description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004817 gas chromatography 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
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- -1 ruthenium salt compounds Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- C25B11/073—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of electrocatalytic materials, and discloses a preparation method and application of a ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst. The material is mainly an electrocatalyst with boron-doped carbon aerogel as a carrier for supporting ruthenium. The preparation method comprises the steps of doping boron into phenolic resin during synthesis of the phenolic resin through a microwave method, carbonizing the phenolic resin at a high temperature after freeze drying to obtain boron-doped carbon aerogel, grinding ruthenium salt and the boron-doped carbon aerogel in a mortar, uniformly mixing, and calcining the mixture in a tube furnace to finally obtain the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst. The invention also discloses application of the catalyst in electrolysis of heavy water. According to the invention, the carbon aerogel with high specific surface area is used as a carrier, so that the catalyst has more active sites, and the reaction is accelerated; electron interactions between boron and ruthenium accelerate D-OD cleavage, reducing D 2 The resulting activation energy of (2) provides the ruthenium-based boron-doped carbon aerogel with alkaline DER activity superior to commercial Pt/C.
Description
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to a preparation method and application of a ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst.
Background
Deuterium is also known as deuterium, symbol D or 2 H, an isotope of hydrogen. Deuterium gas is colorless, odorless, and has an abundance of 0.015% in common hydrogen, and is mostly heavy water D 2 O, the form of deuterium oxide, is present in seawater and normal water. Deuterium is mainly applied to military researches, such as nuclear energy industry, nuclear weapons and the like, and along with the development of times, the application of deuterium is gradually expanded to civil industry, such as optical fiber materials, special lamp sources and the like, and the research on deuterium preparation technology is also of great significance.
Along with the development of technology, more and more deuterium gas preparation technologies are proposed, the application effects of different technologies are different, and only the scientific selection of the preparation technologies can achieve ideal effects. The main deuterium preparation techniques currently exist: liquid hydrogen rectification technology, electrolytic heavy water technology, metal hydride technology, laser technology, gas chromatography technology, and the like.
The reflux of the rectification technology consumes a large amount of energy, and the problem of energy consumption is outstanding, so that the economy is not ideal, and the energy consumption is required to be improved. The purity of deuterium prepared by the flushing chromatography is lower, and the requirement cannot be met, so that the method is less adopted.
The heavy water electrolysis technology adopts a water electrolysis device, and uses deuterium oxide of alkali metal as electrolyte or solid polymer to electrolyze heavy water. The deuterium prepared by the technology has higher purity, and the deuterium with extremely high purity can be obtained only by further purifying the prepared deuterium. The energy consumption problem in the electrolysis process is a major factor affecting the cost, and the main strategies for reducing the working voltage and improving the energy efficiency in the application are as follows: reducing the distance between electrodes, increasing the working pressure, increasing the working temperature, changing the electrode material, etc. Besides electrode materials, other methods can be improved and optimized from engineering, so that it is important to explore a deuterium-separating electrocatalyst with stable performance, low overpotential and proper price.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method and application of a ruthenium-based boron-doped carbon aerogel deuterium-separating catalyst.
The technical scheme provided by the invention is as follows:
the preparation method of the ruthenium-based boron-doped carbon aerogel deuterium-separating catalyst comprises the following specific steps:
1) Weighing a certain amount of resorcinol and boric acid, weighing a certain amount of formaldehyde and deionized water in a microwave tube, and then dripping a certain amount of alkaline solution into the microwave tube to adjust the pH value of the solution in the microwave tube to 8-10; stirring for 30min to fully mix the components in the solution;
2) Placing a microwave tube in a microwave instrument, and solidifying the solution in the microwave tube into red jelly-like solid after reacting for a certain time to obtain boron-doped phenolic resin;
3) The boron-doped phenolic resin is placed in a freeze dryer for freeze drying treatment at a certain temperature;
4) After the freeze drying of the boron-doped phenolic resin is finished, placing the boron-doped phenolic resin in a tube furnace, carbonizing at a high temperature under the protection of nitrogen atmosphere, obtaining boron-doped carbon aerogel after the carbonizing is finished, taking out the boron-doped carbon aerogel, and grinding the boron-doped carbon aerogel by using a mortar;
5) Weighing a certain amount of ruthenium salt and boron-doped carbon aerogel, putting the ruthenium salt and the boron-doped carbon aerogel into a mortar, adding a small amount of absolute ethyl alcohol to further uniformly mix, grinding and uniformly mixing, adding the mixture into a crucible, placing the crucible into a tube furnace to carry out pyrolysis treatment under the protection of nitrogen, and taking out the crucible after the temperature of the crucible is reduced, thus obtaining the ruthenium-based boron-doped carbon aerogel.
As a further technical scheme, the mass ratio of boric acid, resorcinol, formaldehyde and deionized water in the step 1) is 0.7-0.9:15-25:30-40:90-110.
As a further embodiment, the alkaline solution in step 1) is a NaOH solution having a concentration of 1M.
As a further technical scheme, the microwave instrument in the step 2) is set to be at 80 ℃ for 25min and 100W in power; 3) The treatment temperature of freeze drying in the step is minus 58 ℃, and the freeze drying time is 12 h; 4) In the step, the carbonization temperature of the tube furnace is 800 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min.
As a further technical scheme, the ruthenium salt used in the step 5) is one of ruthenium trichloride, triphenylphosphine ruthenium dichloride, ruthenium acetylacetonate and ruthenium acetate; the mass ratio of the ruthenium salt to the boron-doped carbon aerogel is 1-10:100.
As a further technical scheme, the pyrolysis temperature of the tube furnace in the step 5) is 400-800 ℃, the pyrolysis time is 3h, and the heating rate is 5 ℃/min.
The invention also discloses an application of the ruthenium-based boron-doped carbon aerogel deuterium-separating catalyst in electrolysis of heavy water, and the ruthenium-based boron-doped carbon aerogel deuterium-separating catalyst is prepared according to the preparation method.
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 mixed solution on carbon cloth, and finally drying in an infrared drying lamp to obtain a working electrode; the volume ratio of the Nafion solution to the absolute ethyl alcohol is 0.5-2:9, and is preferably 1:9.
The catalyst prepared by the technology has the following advantages compared with the traditional catalyst:
the carbon aerogel carrier with extremely high specific surface area is obtained after carbonization by adopting phenolic resin as a precursor, and after active component loading, the high specific surface area provides more active sites for deuterium separation reaction, so that the catalyst has lower overpotential, and electrochemical performance tests show that the catalyst can maintain long-time stability under higher current density. The electron interaction between the boron and the ruthenium accelerates the cracking of D-OD and reduces D 2 The resulting activation energy of (2) provides the ruthenium-based boron-doped carbon aerogel with alkaline DER activity superior to commercial Pt/C.
Drawings
FIG. 1 is a schematic illustration of a 10mA/cm electrochemical deuterium evolution reaction of a ruthenium-based boron doped carbon aerogel electrocatalyst prepared in examples 1-5 and a commercial platinum carbon 2 An overpotential contrast map at;
FIG. 2 is a 10mA/cm chart of a ruthenium-based boron-doped carbon aerogel electrocatalyst prepared in examples 6-9 and a commercial platinum carbon electrochemical deuterium evolution reaction 2 An overpotential contrast map at;
FIG. 3 is a ruthenium-based boron-doped carbon aerogel electrocatalyst prepared in examples 10-13 andcommercial platinum carbon electrochemical deuterium evolution reaction 10mA/cm 2 Overpotential contrast plot at.
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 ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst comprises the following steps of (400 ℃):
adding boric acid of 0.085g, resorcinol of 2.202g, formaldehyde of 4mL and deionized water of 11mL into a microwave tube, regulating the pH value of the solution in the microwave tube to 9 by using a 1M NaOH solution, stirring for 30min to fully mix the components in the solution, placing the microwave tube into a microwave instrument, carrying out microwave treatment for 25min at 80 ℃ and 100W, taking out red jelly-like solid in the microwave tube, placing the red jelly-like solid into a freeze dryer, carrying out freeze drying treatment for 12h at-58 ℃, placing the red jelly-like solid into a tube furnace, carbonizing for 3h at 800 ℃ under the protection of nitrogen atmosphere after freeze drying, and grinding the obtained product by using a mortar after the carbonization treatment is finished, thus obtaining the boron-doped carbon aerogel.
Weighing 100 mg boron-doped carbon aerogel and 6.2 mg ruthenium trichloride in a mortar, weighing 1mL absolute ethyl alcohol, adding into the mortar, grinding until the absolute ethyl alcohol volatilizes, pouring into a crucible after scraping, placing the crucible in a tube furnace, and adding N into a furnace 2 The temperature is increased from room temperature to 400 ℃ at the temperature increasing rate of 5 ℃/min under the atmosphere, and the mixture is calcined at constant temperature for 3h and then naturally cooled to the room temperature. And taking out the calcined product and grinding uniformly to obtain the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst.
Example 2: the preparation method of the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst comprises the following steps of (500 ℃):
adding boric acid of 0.085g, resorcinol of 2.202g, formaldehyde of 4mL and deionized water of 11mL into a microwave tube, regulating the pH value of the solution in the microwave tube to 9 through a 1M NaOH solution, stirring for 30min to fully mix the components in the solution, placing the microwave tube into a microwave instrument, carrying out microwave treatment for 25min at 80 ℃ and 100W, taking out the red jelly-like solid in the microwave tube, placing the red jelly-like solid into a freeze dryer, carrying out freeze drying treatment for 12h at-58 ℃, placing the red jelly-like solid into a tube furnace, carbonizing the red jelly-like solid in a nitrogen atmosphere at 800 ℃ for 3h, taking out the red jelly-like solid after the carbonization treatment, and grinding the red jelly-like solid with a mortar to obtain the boron-doped carbon aerogel.
Weighing 100 mg boron-doped carbon aerogel and 6.2 mg ruthenium trichloride in a mortar, weighing 1mL absolute ethyl alcohol, adding into the mortar, grinding until the absolute ethyl alcohol volatilizes, pouring into a crucible after scraping, placing the crucible in a tube furnace, and adding N into a furnace 2 And heating from room temperature to 500 ℃ at a heating rate of 5 ℃/min under the atmosphere, calcining at constant temperature for 3 hours, and naturally cooling to room temperature. And taking out the calcined product and grinding uniformly to obtain the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst.
Example 3: the preparation method of the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst comprises the following steps (600 ℃):
adding 0.085g of boric acid, 2.202g of resorcinol, 4mL of formaldehyde and 11mL of deionized water into a microwave tube, regulating the pH value of the solution in the microwave tube to 9 through a 1M NaOH solution, stirring the solution for 30min to fully mix the components in the solution, placing the microwave tube into a microwave instrument, carrying out microwave treatment at 80 ℃ and 100W for 25min, taking out the red jelly-like solid in the microwave tube, placing the red jelly-like solid into a freeze dryer, carrying out freeze drying treatment at-58 ℃ for 12h, placing the red jelly-like solid into a tube furnace, carbonizing the red jelly-like solid at 800 ℃ for 3h under the protection of nitrogen atmosphere, and grinding the boron-doped carbon aerogel by a mortar after the carbonization treatment is finished.
Weighing 100 mg boron-doped carbon aerogel and 6.2 mg ruthenium trichloride in a mortar, weighing 1mL absolute ethyl alcohol, adding into the mortar, grinding until the absolute ethyl alcohol volatilizes, pouring into a crucible after scraping, placing the crucible in a tube furnace, and adding N into a furnace 2 And heating from room temperature to 600 ℃ at a heating rate of 5 ℃/min under the atmosphere, calcining at constant temperature for 3 hours, and naturally cooling to room temperature.And taking out the calcined product and grinding uniformly to obtain the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst.
Example 4: the preparation method of the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst comprises the following steps of (700 ℃):
adding 0.085g of boric acid, 2.202g of resorcinol, 4mL of formaldehyde and 11mL of deionized water into a microwave tube, regulating the pH value of the solution in the microwave tube to 9 through a 1M NaOH solution, stirring the solution for 30min to fully mix the components in the solution, placing the microwave tube into a microwave instrument, carrying out microwave treatment at 80 ℃ and 100W for 25min, taking out the red jelly-like solid in the microwave tube, placing the red jelly-like solid into a freeze dryer, carrying out freeze drying treatment at-58 ℃ for 12h, placing the red jelly-like solid into a tube furnace, carbonizing the red jelly-like solid at 800 ℃ in a nitrogen atmosphere for 3h, and grinding the obtained product by a mortar after the carbonization treatment is finished to obtain the boron-doped carbon aerogel.
Weighing 100 mg boron-doped carbon aerogel and 6.2 mg ruthenium trichloride in a mortar, weighing 1mL absolute ethyl alcohol, adding into the mortar, grinding until the absolute ethyl alcohol volatilizes, pouring into a crucible after scraping, placing the crucible in a tube furnace, and adding N into a furnace 2 And heating from room temperature to 700 ℃ at a heating rate of 5 ℃/min under the atmosphere, calcining at a constant temperature of 3h, and naturally cooling to room temperature. And taking out the calcined product and grinding uniformly to obtain the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst.
Example 5: the preparation method of the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst comprises the following steps of (800 ℃):
adding boric acid of 0.085g, resorcinol of 2.202g, formaldehyde of 4mL and deionized water of 11mL into a microwave tube, regulating the pH value of the solution in the microwave tube to 9 by using a 1M NaOH solution, stirring for 30min to fully mix the components in the solution, placing the microwave tube into a microwave instrument, carrying out microwave treatment for 25min at 80 ℃ and 100W, taking out red jelly-like solid in the microwave tube, placing the red jelly-like solid into a freeze dryer, carrying out freeze drying treatment for 12h at-58 ℃, placing the red jelly-like solid into a tube furnace, carbonizing for 3h at 800 ℃ under the protection of nitrogen atmosphere after freeze drying, and grinding the obtained product by using a mortar after the carbonization treatment is finished, thus obtaining the boron-doped carbon aerogel.
Weighing 100 mg boron-doped carbon aerogel and 6.2 mg ruthenium trichloride in a mortar, weighing 1mL absolute ethyl alcohol, adding into the mortar, grinding until the absolute ethyl alcohol volatilizes, pouring into a crucible after scraping, placing the crucible in a tube furnace, and adding N into a furnace 2 And heating from room temperature to 800 ℃ at a heating rate of 5 ℃/min under the atmosphere, calcining at constant temperature for 3 hours, and naturally cooling to room temperature. And taking out the calcined product and grinding uniformly to obtain the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst.
Examples 6-9A boron carbide-supported ruthenium electrocatalytic deuterium-separating Material and its preparation method (pyrolysis temperature 600 ℃ C.)
Adding boric acid of 0.085g, resorcinol of 2.202g, formaldehyde of 4mL and deionized water of 11mL into a microwave tube, regulating the pH value of the solution in the microwave tube to 9 by using a 1M NaOH solution, stirring for 30min to fully mix the components in the solution, placing the microwave tube into a microwave instrument, carrying out microwave treatment for 25min at 80 ℃ and 100W, taking out the red jelly-like solid in the microwave tube, placing the red jelly-like solid into a freeze dryer, carrying out freeze drying treatment for 12h at-58 ℃, placing the red jelly-like solid into a tube furnace, carbonizing for 3h at 800 ℃ under the protection of nitrogen atmosphere after freeze drying, and grinding the obtained product by using a mortar after the carbonization treatment is finished, thus obtaining the boron-doped carbon aerogel.
Sequentially weighing 100 mg boron-doped carbon aerogel, 2.1 mg ruthenium trichloride (Ru load of 1%, example 6), 100 mg boron-doped carbon aerogel, 6.2 mg ruthenium trichloride (Ru load of 3%, example 7), 100 mg boron-doped carbon aerogel, 10.3 mg ruthenium trichloride (Ru load of 5%, example 8), 100 mg boron-doped carbon aerogel, 14.4 mg ruthenium trichloride (Ru load of 7%, example 9), sequentially adding into a mortar, adding a proper amount of absolute ethyl alcohol, grinding until the absolute ethyl alcohol volatilizes, and then pouring 4 parts of the mixture into 4 separate medicine scrapersIn the crucibles, 4 crucibles were then placed in a tube furnace, in N 2 The temperature is raised from room temperature to 600 ℃ at a heating rate of 5 ℃/min under the atmosphere, and the mixture is calcined at constant temperature of 3h and then naturally cooled to room temperature. And taking out the calcined product and grinding uniformly to obtain the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst.
Examples 10-13 electrocatalytic deuterium-separating material of boron carbide-supported ruthenium and preparation method thereof (load 5%, pyrolysis temperature 600 ℃)
Adding boric acid of 0.085g, resorcinol of 2.202g, formaldehyde of 4mL and deionized water of 11mL into a microwave tube, regulating the pH value of the solution in the microwave tube to 9 by using a 1M NaOH solution, stirring for 30min to fully mix the components in the solution, placing the microwave tube into a microwave instrument, carrying out microwave treatment for 25min at 80 ℃ and 100W, taking out red jelly-like solid in the microwave tube, placing the red jelly-like solid into a freeze dryer, carrying out freeze drying treatment for 12h at-58 ℃, placing the red jelly-like solid into a tube furnace, carbonizing for 3h at 800 ℃ under the protection of nitrogen atmosphere after freeze drying, and grinding the obtained product by using a mortar after the carbonization treatment is finished, thus obtaining the boron-doped carbon aerogel.
Sequentially weighing 100 mg boron-doped carbon aerogel, 10.3 mg ruthenium trichloride (Ru load 5%, example 10), 100 mg boron-doped carbon aerogel, 47.4 mg triphenylphosphine ruthenium dichloride (Ru load 5%, example 11), 100 mg boron-doped carbon aerogel, 19.7 mg ruthenium acetylacetonate (Ru load 5%, example 12), 100 mg boron-doped carbon aerogel, 13.8 mg ruthenium acetate (Ru load 5%, example 13), sequentially adding into a mortar, adding a proper amount of absolute ethyl alcohol, grinding until the absolute ethyl alcohol volatilizes, pouring 4 parts of the mixture into 4 crucibles respectively, placing the 4 crucibles into a tube furnace, and drying in N 2 The temperature is raised from room temperature to 600 ℃ at a heating rate of 5 ℃/min under the atmosphere, and the mixture is calcined at constant temperature of 3h and then naturally cooled to room temperature. And taking out the calcined product and grinding uniformly to obtain the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst.
The above-mentioned working electrodes prepared respectively using the catalysts of examples 1 to 13 and commercial platinum-carbon catalysts (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.
10mA/cm for examples 1-5 2 The overpotential comparison graph is shown in fig. 1, and it is found that when the fixing treatment time is 3h, different pyrolysis temperatures have different effect effects when the fixing treatment time is 3, and the effect is optimal when the heat treatment temperature is 600 ℃. It was found by analysis that this is due to the fact that the pyrolysis temperature is slightly lower at N 2 The pyrolysis decomposition of ruthenium salt is not completely caused under the protection of the catalyst, and the too high temperature can lead to the agglomeration of Ru on the carrier during the reduction, so that large particles are formed and the active center of the surface of the catalyst is reduced.
10mA/cm for examples 6-9 2 The overpotential comparison chart is shown in fig. 2, the optimal effect is found by comparison when the Ru loading is 5%, and the characterization analysis shows that the overpotential of deuterium separation is higher because the active component on the catalyst is too little when the Ru loading is too low; 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.
10mA/cm for examples 10-13 2 The overpotential comparison is shown in FIG. 3, and the comparison of catalysts prepared under the same conditions with different precursor ruthenium salts shows that the effect of different precursors is different when pyrolyzing at high temperature, but the difference is smaller because of the difference of ligands in ruthenium salt compounds, so N at 600 DEG C 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 (7)
1. The preparation method of the ruthenium-based boron-doped carbon aerogel deuterium-separating catalyst is characterized by comprising the following steps of:
1) Weighing a certain amount of resorcinol and boric acid, weighing a certain amount of formaldehyde and deionized water in a microwave tube, and then dripping a certain amount of alkaline solution into the microwave tube to adjust the pH value of the solution in the microwave tube to 8-10; stirring for 30min to fully mix the components in the solution; the mass ratio of the boric acid to the resorcinol to the formaldehyde to the deionized water is 0.7-0.9:15-25:30-40:90-110;
2) Placing a microwave tube in a microwave instrument, and solidifying the solution in the microwave tube into red jelly-like solid after reacting for a certain time to obtain boron-doped phenolic resin;
3) The boron-doped phenolic resin is placed in a freeze dryer for freeze drying treatment at a certain temperature;
4) After the freeze drying of the boron-doped phenolic resin is finished, placing the boron-doped phenolic resin in a tube furnace, carbonizing at a high temperature under the protection of nitrogen atmosphere, obtaining boron-doped carbon aerogel after the carbonizing is finished, taking out the boron-doped carbon aerogel, and grinding the boron-doped carbon aerogel by using a mortar;
5) Weighing a certain amount of ruthenium salt and boron-doped carbon aerogel in a mortar, adding a small amount of absolute ethyl alcohol to further uniformly mix, grinding and uniformly mixing, adding the mixture into a crucible, placing the crucible in a tube furnace for pyrolysis treatment under the protection of nitrogen, and taking out the crucible after the temperature of the crucible is reduced to obtain the ruthenium-based boron-doped carbon aerogel;
the ruthenium salt used in the step 5) is one of ruthenium trichloride, triphenylphosphine ruthenium dichloride, ruthenium acetylacetonate and ruthenium acetate; the mass ratio of ruthenium to boron doped carbon aerogel is 3%, 5% or 7%; the pyrolysis temperature of the tube furnace in the step 5) is 500-700 ℃, the pyrolysis time is 3h, and the heating rate is 5 ℃/min.
2. The method for preparing the ruthenium-based boron-doped carbon aerogel deuterium oxide catalyst according to claim 1, characterized in that the alkaline solution in step 1) is 1M NaOH solution.
3. The method for preparing the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst according to claim 1, characterized in that the microwave instrument in the step 2) is set at a temperature of 80 ℃ for 25min and with a power of 100W; 3) The treatment temperature for freeze-drying in the step was-58℃and the freeze-drying time was 12 h.
4. The method for preparing the ruthenium-based boron-doped carbon aerogel deuterium-precipitating catalyst according to claim 1, wherein in the step 4), the carbonization temperature of a tube furnace is 800 ℃, the carbonization time is 3h, and the heating rate is 5 ℃/min.
5. Use of a ruthenium-based boron-doped carbon aerogel deuterium-separating catalyst in electrolysis of heavy water, characterized in that the ruthenium-based boron-doped carbon aerogel deuterium-separating catalyst is prepared according to the preparation method of any one of claims 1-4.
6. The application of the ruthenium-based boron-doped carbon aerogel deuterium-separating catalyst in electrolysis of heavy water, which is characterized in that 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-separating reaction.
7. The application of the ruthenium-based boron-doped carbon aerogel deuterium oxide catalyst in electrolysis of heavy water, according to claim 6, is characterized in that 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 mixed solution on carbon cloth, and finally drying in an infrared drying lamp to obtain a working electrode; the volume ratio of the Nafion solution to the absolute ethyl alcohol is 0.5-2:9.
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