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RU-2861481-C1 - METHOD FOR CHEMICAL MODIFICATION OF SURFACE OF MULTI-WALLED CARBON NANOTUBES WITH NICKEL(II) SULPHAMATE

RU2861481C1RU 2861481 C1RU2861481 C1RU 2861481C1RU-2861481-C1

Abstract

FIELD: industrial chemistry. SUBSTANCE: invention can be used in the manufacture of supercapacitor electrodes, active material for gas sensors, filler for composite materials, and catalyst supports. A method for chemical modification of the surface of multi-walled carbon nanotubes with nickel sulphamate is proposed. At the first stage, oxygen-containing functional groups are obtained on the surface of multi-walled carbon nanotubes by exposing said nanotubes to nitric acid with a concentration of 60-65% while stirring for 1-6 hours. The diameter of the nanotubes is 10-20 nm, the process temperature is 75-85°C. After this, the carbon nanomaterial is washed with distilled water to pH 6.5-7.5. At the second stage, the material modified with oxygen-containing groups is treated with a solution of nickel sulphamate Ni(NH 2 SO 3 ) 2 with a concentration of 55% for 1-6 hours and washed with distilled water to pH 6.5-7.5. EFFECT: possibility of reducing the number of technological operations during modification of the surface of multi-walled carbon nanotubes. 7 cl, 1 dwg, 1 tbl, 6 ex

Inventors

  • Golovakhin Valerii
  • KURMASHOV PAVEL BORISOVICH
  • Shishin Artem Andreevich
  • Gudyma Tatiana Sergeevna
  • Bannov Aleksandr Georgievich
  • Danilenko Marina Aleksandrovna
  • Lozben Arina Denisovna
  • Smagulova Arina Ruslanovna
  • Shpakova Sofiia Anatolevna

Dates

Publication Date
20260505
Application Date
20250918

Claims (7)

  1. 1. A method for chemically modifying the surface of multi-walled carbon nanotubes with nickel sulfamate, which is carried out as follows: in the first stage, oxygen-containing functional groups are obtained by exposing the surface of multi-walled carbon nanotubes, the diameter of the nanotubes being 10-20 nm, to 100 ml of nitric acid HNO 3 with a concentration of 60-65%, at a process temperature of 75-85°C with constant stirring with a magnetic stirrer coated with fluoroplastic for 1-6 hours, after which the carbon nanomaterial is washed with distilled water to a pH of 6.5-7.5, then in the second stage the material modified with oxygen-containing groups is treated with a solution of nickel sulfamate Ni(NH 2 SO 3 ) 2 with a concentration of 55% for 1-6 hours, after which the carbon nanomaterial is washed with distilled water to a pH of 6.5-7.5.
  2. 2. The method according to paragraph 1, characterized in that the duration of the first and second stages of processing is 1 hour.
  3. 3. The method according to paragraph 1, characterized in that the duration of the first and second stages of processing is 2 hours.
  4. 4. The method according to paragraph 1, characterized in that the duration of the first and second stages of processing is 3 hours.
  5. 5. The method according to paragraph 1, characterized in that the duration of the first and second stages of processing is 4 hours.
  6. 6. The method according to paragraph 1, characterized in that the duration of the first and second stages of processing is 5 hours.
  7. 7. The method according to paragraph 1, characterized in that the duration of the first and second stages of processing is 6 hours.

Description

The proposed invention relates to the technology of processing carbon nanomaterials in the field of nanotechnology, electrochemistry, gas sensorics and can be used for supercapacitor electrodes, active material in gas sensors, nanofiller for various composites and catalyst carrier. A method for producing a metal-containing carbon nanomaterial is known (Russian Federation Patent, RU 2 499 850 C1), in which a film of the metal-containing carbon nanomaterial is formed by sequentially depositing a metal and carbon material onto a dielectric substrate, evaporated in a vacuum. The metal is deposited by thermal evaporation, while the carbon material, in the form of graphite, is deposited onto the substrate by evaporation via a pulsed arc discharge using compensated flows of ionized carbon plasma, stimulated during the deposition process by an inert gas in the form of an ion stream directed perpendicular to the ion gas flow. The metal to be deposited on the substrate is selected from groups including cadmium, a silver-nickel composite, and a silver-nickel-cadmium composite. However, in this method, high-energy metal deposition methods are used to obtain metal particles on the surface; other carbon nanostructures are not considered. Another method for producing a carbon material modified with silver nanoparticles with biocidal properties is known (Russian Federation Patent, RU 2 202 400 C1). The carbon material is modified with silver nanoparticles in several stages, including: preparing a modifying solution of silver nanoparticles, soaking the carbon material in the modifying solution of silver nanoparticles, and washing the carbon material. The modifying solution of silver nanoparticles is an aqueous dispersion obtained from a reverse micellar solution of silver nanoparticles based on a surfactant in a non-polar solvent. The carbon material is soaked in the modifying solution of silver nanoparticles for at least 9 hours and washed with distilled water until the surfactant concentration in the wash water is no more than 0.1 mg/L. However, the method does not indicate other areas of application for such materials, for example, in supercapacitors and catalysis, it does not explain how this material will be used as a biocidal substance, and other carbon nanomaterials are not considered. A method for producing carbon-coated transition metal nanocomposites, their preparation, and application is known (Taiwan Patent, TWI 1791574 B). In the first step, a mixture comprising a transition metal source and a polyvalent organic carboxylic acid is prepared with a solvent to form a homogeneous phase solution. The solvent is then removed from the solution, and the precursor is pyrolyzed in an inert atmosphere. The final step is treatment with a strong acid. This results in a nanocomposite material comprising carbon-coated transition metal particles with a core-shell structure. However, the indicated method uses energy-intensive synthesis methods (pyrolysis at temperatures of 400-800°C), does not show the mechanism of interaction of metal with carbon, does not show the catalytic activity of the resulting material, and does not consider other areas of application, for example, in supercapacitors. A known method, which is a prototype of the proposed invention (Patent CN_111501329_A) and consists in oxidizing the surface of carbon fiber by condensation and refluxing at 60-80 ° C for 2-6 hours using a Soxhlet extractor with strong acids as oxidizing agents, the material is washed with deionized water to pH = 7, dried at 50-70 ° C for 2-4 hours, then the oxidized fiber is immersed in a precipitation bath containing 100 ml of precipitation solution (NiSO 4 ⋅6H 2 O: K 2 S 2 O 6 (O 2 ): H 2 O in a ratio of 1: 0.15-0.2: 25-30), after which an ammonia solution of 5-20 ml is added and stirred until nickel hydroxide is formed on the surface of the carbon fiber, after which it is washed with deionized water to pH = 7, dried at 50-70 °C. In the next step, the carbon fiber modified with nickel hydroxide was immersed in a container with a mixed suspension containing polyether amine/organic solvent for 5-15 min using the impregnation method. The mixed suspension of polyether amine/organic solvent contains from 0.05% to 0.6% polyether amine, from 99.4 wt.% to 99.95 wt.% organic solvent and is dried at a temperature of 50-70 °C. This modification makes it possible to obtain materials with high strength of the interfacial bond between carbon fiber and epoxy composite and improve the electrochemical properties. However, this method allows for the production of nickel (in the form of hydroxide) and amino groups (in the form of polyether amine) through a three-stage surface modification, excluding the cleaning stage, creating a complex composite of three different layers: carbon fibers - nickel hydroxide - polyether amine, while no data are provided on the study of the electrochemical properties of the material. The objective (technical result) of the p