WO2024121604A1 - Procédé thermochimique à base de catalyseurs hétérogènes pour production de matériaux carbonés nanocristallins - Google Patents

Procédé thermochimique à base de catalyseurs hétérogènes pour production de matériaux carbonés nanocristallins Download PDF

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WO2024121604A1
WO2024121604A1 PCT/IB2022/061916 IB2022061916W WO2024121604A1 WO 2024121604 A1 WO2024121604 A1 WO 2024121604A1 IB 2022061916 W IB2022061916 W IB 2022061916W WO 2024121604 A1 WO2024121604 A1 WO 2024121604A1
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process according
carbon
oxygenic
nanocrystalline
ionic
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PCT/IB2022/061916
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English (en)
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Rungkiat NGANGLUMPOON
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Crystallyte Co., Ltd.
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Priority to PCT/IB2022/061916 priority Critical patent/WO2024121604A1/fr
Publication of WO2024121604A1 publication Critical patent/WO2024121604A1/fr

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    • 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
    • C01B32/15—Nano-sized carbon materials
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/26—Preparation

Definitions

  • the present disclosure relates to the production of a carbon nanomaterial, including a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or transition metal, and/or a mixture thereof, particularly when said production of carbon nanomaterials involves heterogeneous catalytic thermochemical reduction.
  • a carbon nanomaterial including a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or transition metal, and/or a mixture thereof, is being consumed at an accelerated rate despite its unavailability in nature.
  • Such consumption trend arises in various fields of applications, especially in the electronics industry, owing to the carbon nanomaterial’s excellent properties such as superior strength and electrical properties.
  • An object of the present invention is to provide a new process for industrially producing a carbon nanomaterial.
  • the inventor has found that embodiments according to the concept of the present invention enable the production of such products at a significantly less energy-intensive condition, as well as satisfactory yield and reaction time.
  • the present invention provides a new process for producing a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or a transition metal, and/or a mixture thereof.
  • Said process comprises thermochemically reducing of an oxygenic carbon source at an atmospheric pressure and an onset temperature within the range of 25 - 100 °C.
  • thermochemical reduction is carried out in presence of: (a) an ionic solution comprising a solvent and an ionic salt, and (b) metallic particles acting as a heterogeneous catalyst, said metallic particles comprising one or more of the following: a post-transition element, a transition element, an oxide, and an alloy thereof.
  • the metal -carbon nanomaterial composite product yield per a single run of an embodiment which depends on the type of the metal catalyst, the oxygenic carbon source and the reaction time, is approximately 10 - 100 g-L ⁇ h" 1 . Such yield is conducive to the scale-up to a mass production scale.
  • the metallic particles comprise one or more of the following: the posttransition element and the transition element.
  • the post-transition element is bismuth (Bi)
  • the transition element is silver (Ag).
  • the size of said metallic particles is within the range of 10 - 1,000 nm.
  • the metallic particles are exposed to the ambient air or oxygen-containing atmosphere at 30 - 125 °C for 30 minutes to 24 hours before the reaction.
  • said oxygenic carbon source is dissolved in the solvent.
  • said oxygenic carbon source is dissolved in the solvent at the concentration within the range of 0. 1 - 10 M.
  • said solvent is a polar solvent.
  • said polar solvent is water.
  • said oxygenic carbon source is water-soluble. More preferably, said oxygenic carbon source is (i) an oxygenic organic compound or (ii) a carbonate salt, a bicarbonate salt or a mixture thereof.
  • oxygenic carbon source is an oxygenic organic compound
  • oxygenic organic compound is a carboxylic acid, an alcohol, a ketone, an aldehyde, or a carbamate.
  • the oxygenic organic compound is a carboxylic acid, it is most preferably acetic acid. In an embodiment where the oxygenic organic compound is an alcohol, it is most preferably ethanol. In an embodiment where the oxygenic organic compound is a ketone, it is most preferably acetone. In an embodiment where the oxygenic organic compound is an aldehyde, it is most preferably acetaldehyde. In an embodiment where the oxygenic organic compound is a carbamate, said carbamate is preferably prepared by saturating a primary amine aqueous solution with CO2; and in such embodiment, it is most preferred that the primary amine is mono ethanolamine and/or that the concentration of the primary amine aqueous solution is within the range of 0. 1 - 10 M.
  • the carbonate salt is most preferably Na2CC>3.
  • the bicarbonate salt is most preferably NH4HCO3.
  • the carbonate salt is preferably prepared by saturating an aqueous solution of a strong base with CO2.
  • the strong base is KOH; also most preferably, the strong base’s concentration in the aqueous solution is within the range of 0.1 - 10 M.
  • the bicarbonate salt is preferably prepared by saturating an aqueous solution of a tertiary amine, or by saturating an ammonia aqueous solution, with CO2. More preferably, the tertiary amine is dimethylethanolamine (DMAE); also more preferably, the tertiary amine’s concentration in the aqueous solution is within the range of 0.1 - 10 M.
  • DMAE dimethylethanolamine
  • the ammonia’s concentration in the aqueous solution is within the range of 0.1 - 10 M.
  • the ionic salt comprises a cation selected from ammonium cation, imidazolium cation, and a mixture thereof.
  • said ammonium cation is ammonium cation (NH4 + ) and choline cation.
  • said imidazolium cation is l-butyl-3- methylimidazolium ([bmim]).
  • the anion of said ionic salt is selected from the group comprising tetrafluoroborate (BEp), hexafluorophosphate (PFr,“). halides (O’, Br, F", I"), hexafluoroantimonate (SbFr>“). sulfate (SOr 2- ). and nitrate (NO ).
  • the most preferable ionic salts are: l-butyl-3- methylimidazolium tetrafluoroborate ([bmim][BF4]) or ammonium sulfate ((NFL ⁇ SCh) or choline chloride.
  • the concentration of said ionic salt in the ionic solution is within the range of 0.1 - 10 M.
  • H2O2 or Fe (II) ions are added to the ionic solution.
  • the present invention provides a process for producing a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or a transition metal, and/or a mixture thereof.
  • Said process comprises steps of: (i) thermochemically reducing an oxygenic carbon source in presence of (a) an ionic solution, and (b) metallic particles suspended in said ionic solution and acting as a heterogeneous catalyst; and (ii) stirring said ionic solution.
  • Said ionic solution comprises a mixture of (a) 1- butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), ammonium sulfate ((NH4)2SO4) or choline chloride, and (b) water.
  • Said thermochemically reducing the oxygenic carbon source occurs at an atmospheric pressure and an onset temperature within the range of 25 - 100 °C.
  • step of (ii), stirring the ionic solution may be carried out before or during the thermochemical reduction and may be carried out continuously or intermittently.
  • the ionic solution is stirred continuously during the thermochemical reduction.
  • Fig. 1 shows a schematic diagram of a thermochemical reactor for thermochemically reducing an oxygenic carbon source in accordance with a preferred embodiment (not to scale).
  • Fig. 2A shows a Raman spectrum exhibiting merged peaks of a product of Example 1.
  • Fig. 2B shows a matching of d-spacing, as obtained from Selected Area Electron Diffraction (SAED), of the product of Example 1.
  • Fig. 2C shows a first Transmission Electron Microscopy (TEM) image of the product of Example 1.
  • Fig. 2D shows a second Transmission Electron Microscopy (TEM) image of the product of Example 1.
  • Fig. 2E shows Energy Dispersive X-ray (EDX) peaks of the product of Example 1.
  • Fig. 3A shows a Raman spectrum exhibiting merged peaks of a product of Example 2.
  • Fig. 3B shows a matching of d-spacing, as obtained from Selected Area Electron Diffraction (SAED), of the product of Example 2.
  • Fig. 3C shows a first Transmission Electron Microscopy (TEM) image of the product of Example 2.
  • Fig. 3D shows a second Transmission Electron Microscopy (TEM) image of the product of Example 2.
  • Fig. 3E shows Energy Dispersive X-ray (EDX) peaks of the product of Example 2.
  • Fig. 4A shows a Raman spectrum exhibiting merged peaks of a product of Example 3.
  • Fig. 4B shows a matching of d-spacing, as obtained from Selected Area Electron Diffraction (SAED), of the product of Example 3.
  • Fig. 4C shows a first Transmission Electron Microscopy (TEM) image of the product of Example 3.
  • Fig. 4D shows a second Transmission Electron Microscopy (TEM) image of the product of Example 3.
  • Fig. 4E shows Energy Dispersive X-ray (EDX) peaks of the product of Example 3.
  • Fig. 5 shows a Raman spectrum exhibiting merged peaks of a product of Example 4.
  • Fig. 6 shows a Raman spectrum exhibiting merged peaks of a product of Example 5.
  • Fig. 7 shows a Raman spectrum exhibiting merged peaks of a product of Example 6.
  • Fig. 8 shows a Raman spectrum exhibiting merged peaks of a product of Example 7.
  • Fig. 9 shows a Raman spectrum exhibiting merged peaks of a product of Example 8.
  • Fig. 10 shows a Raman spectrum exhibiting merged peaks of a product of Example 9.
  • Fig. 11 shows a Raman spectrum exhibiting merged peaks of a product of Example 10.
  • Fig. 12 shows a Raman spectrum exhibiting merged peaks of a product of Example 11.
  • Fig. 13 shows a Raman spectrum exhibiting merged peaks of a product of Example 12.
  • Fig. 14 shows a Raman spectrum exhibiting merged peaks of a product of Example 13.
  • Fig. 15 shows a Raman spectrum exhibiting merged peaks of a product of Example 14.
  • Fig. 16 shows a Raman spectrum exhibiting merged peaks of a product of Example 15.
  • compositions and processes include the recited elements, but not excluding others.
  • Consisting essentially of when used to define compositions and methods, shall mean excluding other elements of any essential significance to the combination for the stated purpose. Thus, a process or product consisting essentially of the elements as defined herein would not exclude other materials or steps that do not materially affect the basic and novel characteristic(s) of the claimed invention.
  • Consisting of shall mean excluding more than trace elements of other ingredients and substantial steps. Embodiments defined by each of these transition terms are within the scope of this invention.
  • Oxygenic carbon source is intended to mean a mono-molecular compound or an ionic compound containing both carbon and oxygen atoms.
  • Oxygenic organic compound is intended to mean a mono-molecular organic compound having an oxygen atom.
  • Fig. 1 shows a schematic diagram of a thermochemical reactor in which a process for producing a carbon nanomaterial is conducted in accordance with a preferred embodiment.
  • the thermochemical reactor (10) comprises a receptacle (100), a heating element (200), a stirrer (300), and a vent (400).
  • the receptacle (100) contains an ionic solution (110) in which metallic particles (120) are present and act as a heterogeneous catalyst.
  • the ionic solution (110) is a mixture of an ionic salt and a solvent in which an oxygenic carbon source is dissolved.
  • the heating element (200), the source of thermal energy is preferably connected to the lower part or the bottom of the receptacle (100) and configured to heat the ionic solution (110).
  • the stirrer (300) is preferably disposed so as to immerse in the ionic solution (110) and configured to disperse the metallic particles (120) in the ionic solution (110).
  • the stirrer (300) takes the form of a propeller having a shaft (310), an end of which is connected to multiple blades (320), and another end of which, to a motor (330).
  • the shaft (310) is disposed substantially vertically so that the blades (320) are effectively immersed in the ionic solution (110) and the motor (330) is located away from the ionic solution (110).
  • the vent (400), through which the gaseous byproducts leave the receptacle (100), is preferably located at the top of the receptacle (100).
  • the carbon source is an oxygenic carbon source.
  • a water-soluble oxygenic carbon source is used.
  • the oxygenic carbon source is a carbonate salt or a bicarbonate salt.
  • Preferred carbonate and bicarbonate salts include: Na2CO and NH4HCO3.
  • the carbonate salt is prepared by saturating an aqueous solution of a strong base with CO2.
  • the bicarbonate salt is prepared by saturating (i) an ammonia aqueous solution or (ii) an aqueous solution of a tertiary amine, with CO2.
  • the concentration of the strong base, ammonia, or the tertiary amine, in their respective aqueous solution is within the range of 0.1 - 10 M.
  • the oxygenic carbon source is an oxygenic organic compound.
  • Preferred oxygenic organic compounds include: an alcohol, carboxylic acid, ketone, aldehyde, and carbamate.
  • the carbamate is prepared by saturating primary amine aqueous solution with CO2. More preferably, the primary amine is mono ethanolamine and/or the concentration of the primary amine aqueous solution is within the range 0.1 - 10 M.
  • the oxygenic carbon source may be supplied to the ionic solution in any desired form, for example, in the solid, liquid, gaseous, or solvated form, depending on the phase stability at the operating temperature and pressure.
  • the oxygenic carbon source is dissolved in the ionic solution (i.e., supplied in the solvated form).
  • a process according to the concept of the present invention may be carried out in various conditions which may be adjusted according to the circumstantial requirements.
  • the applicable pressure is within the range of about 1 to about 20 atm.
  • the pressure in accordance with the preferred embodiment is an ambient pressure.
  • the ambient pressure refers to a common or usual condition surrounding any person in a room.
  • An ambient pressure for operating the process is preferably 1 atm. Because a process in accordance with the preferred embodiment allows the catalytic thermochemical reduction to occur effectively at such ambient pressure, it obviates the need to pressurize, depressurize, vacuumize or control the pressure at any part of the thermochemical reactor (10) and thus substantially simplifies the production.
  • the onset temperature of the thermochemical reactor (10) is at least of the thermal energy sufficient to initiate the catalytic thermochemical reduction of the oxygenic carbon source.
  • the onset temperature of the ionic solution (110) is substantially constant during the catalytic thermochemical reduction.
  • thermochemical reactor (10) depends on the carbon source and the metallic particles being selected.
  • the thermochemical reactor (10) comprises a heating element (200) to provide the onset temperature, which is preferably within a range of about 25 - 100 °C.
  • the heating element (200) is adapted to monitor and control the onset temperature.
  • the catalytic thermochemical reduction occurred in an autoclave which is capable of both monitoring and regulating the onset temperature.
  • the autoclave is commonly used as an industry-scale thermochemical reactor, which is applicable to the concept of the present invention.
  • the ionic solution (110) comprises a solvent and an ionic salt.
  • the solvent is a polar solvent, and more preferably is water.
  • ionic salts may be part of the mixture that forms the ionic solution (110).
  • the ionic salts in an embodiment are compounds represented by Formula (I):
  • n ‘ is selected from the group comprising tetrafluoroborate (
  • [A] + is selected from —
  • R 1 , R 2 , R 3 , and R 4 being selected from hydrogen atom, Cl-C6-alkyl, Cl-C6-alkoxy, Cl- C6-aminoalkyl, Cl-C6-hydroxylalkyl, C5-C12-aryl, and C5-C12-aryl-Cl-C6-alkyl groups; and
  • R, R 1 , and R 2 being selected from Cl-C6-alkyl, Cl-C6-alkoxy, Cl-C6-aminoalkyl, C5- C12-aryl, and C5-C12-aryl-Cl-C6-alkyl groups.
  • the preferred combination of the ionic salt, the oxygenic carbon source, and water is as follows: (a) the ionic salt being a mixture of l-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), ammonium sulfate ((NH ⁇ SCh) or choline chloride, (b) an oxygenic carbon source, and (c) water.
  • the ionic salt also functions as a stabilizer of nanoparticles/carbon nanomaterial formed at the metallic particles (120) during the catalytic thermochemical reduction of the oxygenic carbon source in the thermochemical reactor (10).
  • the ionic salt is selected from ([bmim][BF4]), (NFL ⁇ SCh, and choline chloride.
  • the metallic particles (120) act as a heterogeneous catalyst for the catalytic thermochemical reduction.
  • the metallic particles (120) comprise one or more of the following: the posttransition element and the transition element. More preferably, the post-transition element is Bi and the transition element is Ag.
  • the size of the metallic particles is within the range of 10 - 1,000 nm.
  • the metallic particles are exposed to the ambient air or oxygencontaining atmosphere at 30 - 125 °C for 30 minutes to 24 hours in order to create a thin oxide layer before the start of thermochemical reduction.
  • the catalytic thermochemical reduction occurs in the thermochemical reactor (10) as a batch operation.
  • the crystal structure and crystal size of the resulting product depends on the nature of metallic particles (120), the carbon source used, the energy supplied, and the reaction time, among others. Prolonging the reaction time results in a larger crystallite size being formed.
  • the reaction time for each batch of production can be ranged from about 5 minutes to 300 minutes. Preferably, the reaction time for each batch of production is about 15 minutes to 75 minutes.
  • Nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite said composite containing a post-transition metal or a transition metal, and/or a mixture thereof
  • the process for producing a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or a transition metal, and/or mixture thereof in the thermochemical reactor (10) is a batch operation.
  • nanocrystalline carbon with the ID, 2D, or 3D structure and/or the nanocrystalline diamond and/or the amorphous carbon and/or the metal-carbon nanomaterial composite, said composite containing a post-transition metal or transition metal, and/or the mixture thereof is formed at the metallic particles (120).
  • the carbon product obtained from a process in accordance with a preferred embodiment comprises a graphite and/or a graphene and/or a graphitic carbon and/or the nanocrystalline diamond and/or the amorphous carbon, and/or the metal-carbon nanomaterial composite, said composite containing the post-transition metal or the transition metal, and/or the mixture thereof.
  • the carbon product being produced is further separated from the metallic particles (120) by a known separation process.
  • said separation process is a mechanical removal process, such as mechanical abrasion, or ultrasonication.
  • the carbon product may contain metallic material residues, which can be further removed from the carbon product by means of a conventional chemical removal process, preferably acid leaching.
  • acid leaching involves the use of nitric acid (HNO3), hydrochloric acid (HC1), or a mixture thereof.
  • the separation process of the carbon product from the metallic particles (120) comprises the following steps:
  • step (2) placing the solid product that was removed by step (1) in a microcentrifuge tube
  • the mixture of nitric acid and hydrochloric acid is in a molar ratio of 1:3 in 0.3 ml of the solution
  • DI water deionized water
  • a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon product and/or a metal- carbon nanomaterial composite said composite containing a post-transition metal or a transition metal, and/or a mixture thereof, which is a mixture having various carbon structures.
  • Said structures are inclusive of, and selectable from: an amorphous carbon, a graphite, a graphene, a nanocrystalline diamond, and a metal-carbon nanomaterial composite, said composite containing a post-transition metal or a transition metal.
  • thermochemical reactor 10
  • the thermochemical reactor (10) further contained the ionic solution (110), the onset temperature of which was generated and measured by the heating element (200).
  • the ionic solution (110) was dispersed with the metallic particles (120) and stirred by the stirrer (300) at the agitation rate of 10 - 1,000 rpm.
  • the reaction was carried out under a pressure of about 1 atm. After the reaction time, the carbon nanomaterial product was formed at the metallic particles (120), which was then removed from the ionic solution (110) and dried.
  • the metallic particles (120) were exposed to the ambient air or oxygencontaining atmosphere at 30 - 125 °C for 30 minutes to 24 hours before being used in the thermochemical reduction.
  • Some oxygenic carbon sources were prepared by saturating the ionic solution (110) with carbon dioxide gas (CO2) at ambient conditions. More particularly, where the oxygenic carbon source was a carbonate salt, the ionic solution (110) contained KOH (a strong base); where the oxygenic carbon source was a bicarbonate salt, the ionic solution (110) contained ammonia or dimethylethanolamine (a tertiary amine); where the oxygenic carbon source was a carbamate, the ionic solution (110) contained mono ethanolamine (a primary amine).
  • the flow rate of CO 2 per volume of the ionic solution (110) was within the range of 0.04 - 40 cm 3 CO2 per cm 3 ionic solution per minute.
  • the CO2 purging time was within 1-1,000 minutes.
  • Table 1 in the next sheet shows the particulars of Examples 1-15. Description of the product obtained from each Example shall follow Table 1.
  • Example 1 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure.
  • Fig. 2A shows the Raman spectrum of the product of Example 1.
  • SAED Selected Area Electron Diffraction
  • TEM Transmission Electron Microscopy
  • EDX Energy Dispersive X-ray
  • Example 2E revealed the following atomic percentages of said product: 91.34 % carbon; 1.65 % oxygen; 1.86 % copper; 0.5 % silver; 0.33 % iodine; and 4.31 % mercury. All the foregoing results confirmed that the product of Example 1 comprised nanocrystalline diamond comprising n-diamond, hexagonal diamond, i-Carbon, graphitic carbon, and amorphous carbon structures.
  • Example 2 produced a metal-carbon composite product in the form of nanocrystalline carbon with a 2D structure.
  • Fig. 3A shows the Raman spectrum of the product of Example 2.
  • SAED Selected Area Electron Diffraction
  • TEM Transmission Electron Microscopy
  • EDX Energy Dispersive X-ray
  • Example 3 produced a metal -carbon composite product in the form of metallic Bi/Bi oxides and nanocrystalline carbon with a ID, 2D, and 3D structure.
  • Fig. 4A shows the Raman spectrum of the product of Example 3.
  • SAED Selected Area Electron Diffraction
  • TEM Transmission Electron Microscopy
  • EDX Energy Dispersive X-ray
  • Example 4E revealed the following atomic percentages of said product: 53.34 % carbon; 27.1 % oxygen; 3.44 % fluorine; 15.19 % tin; and 0.93 % bismuth. All the foregoing results confirmed that the product of Example 3 comprised graphitic carbon, and amorphous carbon structures.
  • Example 4 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 5, as observed from the shown Raman spectrum, the carbon product obtained from Example 4 comprised graphitic carbon, and amorphous carbon structures.
  • Example 5 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 6, as observed from the shown Raman spectrum, the carbon product obtained from Example 5 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
  • Example 6 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 7, as observed from the shown Raman spectrum, the carbon product obtained from Example 6 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
  • Example 7 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 8, as observed from the shown Raman spectrum, the carbon product obtained from Example 7 comprised graphitic carbon, and amorphous carbon structures.
  • Example 8 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 9, as observed from the shown Raman spectrum, the carbon product obtained from Example 8 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
  • Example 9 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 10, as observed from the shown Raman spectrum, the carbon product obtained from Example 9 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
  • Example 10 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 11, as observed from the shown Raman spectrum, the carbon product obtained from Example 10 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
  • Example 11 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure.
  • the carbon product obtained from Example 11 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
  • Example 12 produced a metal -carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure.
  • the carbon product obtained from Example 12 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
  • Example 13 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 14, as observed from the shown Raman spectrum, the carbon product obtained from Example 13 comprised graphitic carbon, and amorphous carbon structures.
  • Example 14 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 15, as observed from the shown Raman spectrum, the carbon product obtained from Example 14 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
  • Example 15 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 16, as observed from the shown Raman spectrum, the carbon product obtained from Example 15 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.

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Abstract

L'invention concerne un nouveau procédé de production d'un carbone nanocristallin à structure 1D, 2D ou 3D et/ou d'un diamant nanocristallin et/ou d'un carbone amorphe et/ou d'un composite métal-carbone nanomatériau, ledit composite contenant un métal post-transition ou un métal de transition, et/ou un mélange de ceux-ci, par réduction thermochimique d'une source de carbone oxygénique à une pression atmosphérique et à une température de départ comprise entre 25 et 100 °C en présence (a) d'une solution ionique comprenant un solvant et un sel ionique, et (b) de particules métalliques jouant le rôle de catalyseur hétérogène. Lesdites particules métalliques comprennent un ou plusieurs des éléments suivants : un élément de post-transition, un élément de transition, un oxyde et un de leurs alliages. La pression atmosphérique et la faible température d'amorçage permises par les modes de réalisation simplifient la production, et le rendement en carbone nanocristallin peut être augmenté pour atteindre une échelle de production de masse. Un produit obtenu selon le nouveau procédé comprend un carbone nanocristallin ayant une structure 1D, 2D ou 3D et/ou un diamant nanocristallin et/ou un carbone amorphe et/ou un composite de nanomatériau métal-carbone, ledit composite contenant un métal de post-transition ou un métal de transition. Un tel produit peut être un mélange qui contient diverses structures de carbone, comprenant : un diamant nanocristallin, un carbone amorphe, un carbone graphitique et un composite de nanomatériau métal-carbone, ledit composite contenant un métal de post-transition ou un métal de transition. Ledit produit peut en outre comprendre un graphite ou un graphène.
PCT/IB2022/061916 2022-12-08 2022-12-08 Procédé thermochimique à base de catalyseurs hétérogènes pour production de matériaux carbonés nanocristallins WO2024121604A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050079118A1 (en) 2002-02-13 2005-04-14 Shigeo Maruyama Process for producing single-walled carbon nanotube, single-walled carbon nanotube, and composition containing single-walled carbon nanotube
WO2013158155A1 (fr) 2012-04-16 2013-10-24 Seerstone Llc Procédés d'utilisation de catalyseurs métalliques dans les convertisseurs catalytiques d'oxyde de carbone
CN110015660A (zh) * 2018-11-19 2019-07-16 华南理工大学 一种银掺杂木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用
CN114558575A (zh) * 2022-03-14 2022-05-31 武汉科技大学 一种秸秆分级制备生物炭双金属催化剂和木质素荧光碳点的方法及其水处理应用
WO2022185098A1 (fr) * 2021-03-04 2022-09-09 Crystallyte Co., Ltd. Procédé électrolytique pour produire un carbone nanocristallin avec une structure 1d, 2d, ou 3d et/ou un diamant nanocristallin et/ou un carbone amorphe et/ou un composite de nanomatériau métal-carbone et/ou un mélange de ceux-ci dans des conditions ambiantes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050079118A1 (en) 2002-02-13 2005-04-14 Shigeo Maruyama Process for producing single-walled carbon nanotube, single-walled carbon nanotube, and composition containing single-walled carbon nanotube
WO2013158155A1 (fr) 2012-04-16 2013-10-24 Seerstone Llc Procédés d'utilisation de catalyseurs métalliques dans les convertisseurs catalytiques d'oxyde de carbone
CN110015660A (zh) * 2018-11-19 2019-07-16 华南理工大学 一种银掺杂木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用
WO2022185098A1 (fr) * 2021-03-04 2022-09-09 Crystallyte Co., Ltd. Procédé électrolytique pour produire un carbone nanocristallin avec une structure 1d, 2d, ou 3d et/ou un diamant nanocristallin et/ou un carbone amorphe et/ou un composite de nanomatériau métal-carbone et/ou un mélange de ceux-ci dans des conditions ambiantes
CN114558575A (zh) * 2022-03-14 2022-05-31 武汉科技大学 一种秸秆分级制备生物炭双金属催化剂和木质素荧光碳点的方法及其水处理应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LU ZHIWEI ET AL: "Facile one-step fabrication of a novel 3D honeycomb-like bismuth nanoparticles decorated N-doped carbon nanosheet frameworks: Ultrasensitive electrochemical sensing of heavy metal ions", ELECTROCHIMICA ACTA, ELSEVIER, AMSTERDAM, NL, vol. 266, 31 January 2018 (2018-01-31), pages 94 - 102, XP085355603, ISSN: 0013-4686, DOI: 10.1016/J.ELECTACTA.2018.01.188 *

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