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CN-122013237-A - Preparation method of carbon-supported ruthenium/ruthenium dioxide two-dimensional nanosheet

CN122013237ACN 122013237 ACN122013237 ACN 122013237ACN-122013237-A

Abstract

The invention discloses a preparation method of a carbon-loaded ruthenium/ruthenium dioxide two-dimensional nano sheet, which mainly comprises the steps of adding inorganic ruthenium salt into inorganic carbonate, uniformly mixing, putting into a drying oven, drying for at least 12 hours to prepare a salt material, heating the uniformly mixed salt material to a target temperature in a crucible by inert atmosphere in a vertical tubular resistance furnace, introducing Ar gas into the crucible, fully stirring to form stable liquid molten salt, then lowering an electrode to a designated position below the liquid surface of the molten salt under a two-electrode system consisting of a non-carbon anode and a conductive cathode for long-time pulse voltage electrolysis, after the electrolysis is completed, lifting the electrode from the liquid surface of the molten salt, peeling off a cathode product after the temperature of the furnace is reduced to room temperature, and repeatedly cleaning by deionized water and dilute hydrochloric acid to directly obtain the carbon-loaded ruthenium/ruthenium dioxide two-dimensional nano sheet. The preparation method has the advantages of short preparation flow, low requirement on equipment, environment-friendly process, no emission of harmful three wastes, flexibility, convenience, easy realization and meeting the requirements of green manufacturing strategy.

Inventors

  • CHEN YUNFEI
  • RONG WAN

Assignees

  • 西北有色金属研究院

Dates

Publication Date
20260512
Application Date
20260227

Claims (9)

  1. 1. The preparation method of the carbon-supported ruthenium/ruthenium dioxide two-dimensional nanosheet is characterized by comprising the following steps of: Adding inorganic ruthenium salt into inorganic carbonate, uniformly mixing, and then placing into a vacuum drying oven for drying to obtain a uniformly mixed salt material; Heating the uniformly mixed salt material obtained in the first step to a target temperature in a crucible in a vertical tubular resistance furnace by inert atmosphere, introducing Ar gas into a molten pool formed by the uniformly mixed salt material by adopting a corundum tube, fully stirring to form stable liquid molten salt, and then under a two-electrode system consisting of a non-carbon anode and a conductive cathode, lowering an electrode to a designated position below the liquid surface of the molten salt for long-time pulse voltage electrolysis; And thirdly, after the electrolysis in the second step is completed, the electrode is lifted off the molten salt liquid level, the cathode product is peeled off after the furnace temperature is reduced to room temperature, and the carbon-loaded ruthenium/ruthenium dioxide two-dimensional nano-sheet is directly obtained after repeated cleaning by deionized water and dilute hydrochloric acid.
  2. 2. The preparation method of the carbon-supported ruthenium/ruthenium dioxide two-dimensional nano sheet is characterized in that in the first step, the inorganic ruthenium salt is RuCl 3 、RuCl 3 ·nH 2 O、K 2 RuCl 6 or Na 2 RuCl 5 ·nH 2 O, and the addition amount of the inorganic ruthenium salt is 5% -10% of the mass of the uniformly mixed salt material.
  3. 3. The preparation method of the carbon-supported ruthenium/ruthenium dioxide two-dimensional nano sheet according to claim 1, wherein in the first step, the inorganic carbonate is any two of Na 2 CO 3 、Li 2 CO 3 、K 2 CO 3 、CaCO 3 、MgCO 3 and BaCO 3 , the addition amount of the inorganic carbonate is 90% -95% of the mass of the uniformly mixed salt material, the drying temperature is above 100 ℃, and the time is not less than 12 hours.
  4. 4. The preparation method of the carbon-supported ruthenium/ruthenium dioxide two-dimensional nano sheet according to claim 1, wherein in the second step, the non-carbon anode is a NiFe 2 O 4 base rod, a TiB 2 base rod, a SnO 2 rod or a RuO 2 •TiO 2 rod, the diameter of the non-carbon anode is not less than 10mm, and the conductive cathode is a stainless steel sheet, a nickel sheet or a titanium sheet and has a thickness not exceeding 1mm.
  5. 5. The method for preparing a carbon-supported ruthenium/ruthenium dioxide two-dimensional nano-sheet according to claim 1, wherein polishing pretreatment is performed on sand paper with a particle size of not less than 1500 meshes before the conductive cathode is used in the second step.
  6. 6. The method for preparing the carbon-supported ruthenium/ruthenium dioxide two-dimensional nano-sheet according to claim 1, wherein the target temperature in the second step is 700-800 ℃, and the duration of Ar gas introducing stirring is not less than 10min.
  7. 7. The method for preparing the carbon-supported ruthenium/ruthenium dioxide two-dimensional nanosheets according to claim 1, wherein in the second step, the pulse voltage of the non-carbon anode relative to the conductive cathode during electrolysis is set to be 4.0-6.0V at a high voltage, 2.5-4.0V at a low voltage, and 1 s-5 s at a pulse width, and the total electrolysis duration is not less than 6h.
  8. 8. The method for preparing the carbon-supported ruthenium/ruthenium dioxide two-dimensional nano-sheet according to claim 1, wherein the designated position in the second step is not more than 20mm below the molten salt liquid level, and the descending depth of the non-carbon anode is not less than the descending depth of the conductive cathode.
  9. 9. The method for preparing a carbon-supported ruthenium/ruthenium dioxide two-dimensional nano-sheet according to claim 1, wherein the thickness of the carbon-supported ruthenium/ruthenium dioxide two-dimensional nano-sheet in the third step is not more than 50nm.

Description

Preparation method of carbon-supported ruthenium/ruthenium dioxide two-dimensional nanosheet Technical Field The invention belongs to the technical field of electrochemistry, in particular to the field of molten salt electrochemistry for preparing micro-nano materials, and particularly relates to a preparation method of a carbon-supported ruthenium/ruthenium dioxide two-dimensional nano sheet. Background With the continuous development of society, green sustainable energy utilization is paid attention to by all parties, and efficient conversion and storage of energy are increasingly urgent. Functional materials with catalysis, energy storage and the like are indispensable in the process of energy catalytic conversion and storage. The carbon-supported ruthenium-based functional powder not only maintains high reactivity and capability conversion energy storage capability, but also saves cost. Particularly, the carbon-supported ruthenium/ruthenium dioxide nano powder is used as an electrolyzed water catalyst, and has good difunctional catalytic hydrogen evolution and oxygen evolution activities in the hydrogen production by the electrolysis of water (Chinese patent: application number 202110037579.9). In addition, carbon-supported ruthenium/ruthenium dioxide exhibits high capacity, rapid charge storage performance as an electrode material in emerging energy storage device supercapacitors (Mukesh Kumar, kamal k. Kar, pradip paik. Chemical ENGINEERING JOURNAL, 2024, 499: 156414.). However, the synthesis methods of the carbon-supported ruthenium/ruthenium dioxide have the problems of complex precursor reagent, high process control difficulty, obvious three-waste emission and the like. Therefore, the adoption of the green electrochemical molten salt electrochemical technology for controllably preparing the high-value functional powder has important significance. In addition, two-dimensional nanoplatelet structures often have ultra-high specific surface areas, excellent mechanical properties, electronic properties, interfacial effects, and the like. Providing more active sites, improving the reaction efficiency (such as MoS 2 for catalyzing hydrogen evolution). Has great advantages in the aspects of providing more active sites, improving the reaction efficiency, increasing the contact area of an electrode and an electrolyte, improving the performance of a battery/super capacitor and the like. Therefore, the controllable preparation of the carbon-supported ruthenium/ruthenium dioxide two-dimensional nano-sheet has the value of promoting the excellent performance of the functional material. At present, the preparation of the carbon-supported ruthenium/ruthenium dioxide two-dimensional nano-sheet by molten salt electrolysis is rarely reported. Therefore, a green, simple and highly controllable preparation method of the carbon-supported ruthenium/ruthenium dioxide two-dimensional nano-sheet by molten salt electrolysis is needed to be based on the molten salt electrolysis technology. Disclosure of Invention The invention aims to solve the technical problem of providing a preparation method of a carbon-supported ruthenium/ruthenium dioxide two-dimensional nano sheet aiming at the defects of the prior art. The method is based on raw material control of inorganic ruthenium salt and carbonate, fully coordinates electrolysis parameters including parameters such as electrolysis temperature, pulse voltage, electrolysis duration, electrode surface state and the like, establishes ruthenium and carbon cooperative co-electrodeposition, controls reduction degree of carbon and ruthenium and template deposition effect, forms a two-dimensional nano sheet structure of carbon-loaded ruthenium/ruthenium dioxide, basically has no discharge of polluting waste gas and waste liquid in the electrolysis process, and meets the development requirement of current low-carbon green recycling economy. In order to solve the technical problems, the technical scheme adopted by the invention is that the preparation method of the carbon-supported ruthenium/ruthenium dioxide two-dimensional nanosheet is characterized by comprising the following steps of: Adding inorganic ruthenium salt into inorganic carbonate, uniformly mixing, and then placing into a vacuum drying oven for drying to obtain a uniformly mixed salt material; Heating the uniformly mixed salt material obtained in the first step to a target temperature in a crucible in a vertical tubular resistance furnace by inert atmosphere, introducing Ar gas into a molten pool formed by the uniformly mixed salt material by adopting a corundum tube, fully stirring to form stable liquid molten salt, and then under a two-electrode system consisting of a non-carbon anode and a conductive cathode, lowering an electrode to a designated position below the liquid surface of the molten salt for long-time pulse voltage electrolysis; And thirdly, after the electrolysis in the second step is completed, the electrode