Water, bubble collapse and syngas species in the synthesis of graphene and its derivatives

Abstract

Hydrodynamic cavitation-inducing inertial, non-inertial, and combination reactors are employed in the hydrothermal synthesis of graphene and its derivatives, both in solution and vapor. Various hydrodynamic cavitation reactor embodiments are revealed. Water is used to both nucleate and “self-heal” graphene sheet growth in solution and vapor. Various methods of combustion, hydrothermal and dehydration synthesis of graphene and its derivatives are revealed. Additionally, water and ice are used as a substrate, both alone and in combination with other substrates, to grow and recover useful graphene and its derivatives.

What is claimed is: 
     
         1 . A method of graphene synthesis, comprising:
 (a) creation of synthesis gas species from the hydrothermal heating of a carbonaceous material in a reaction chamber;   (b) collection, direction and removal of the resulting vapors from the reaction chamber to a substrate; and   (c) deposition of graphene on the surface of the substrate.   
     
     
         2 . The method of  claim 1 , wherein the substrate comprises water. 
     
     
         3 . The method of  claim 2 , further comprising application of sonication, ultrasonication, surfactant, oxidizing agents, reducing agents, ionizing irradiation, pH adjustment, pressurization, depressurization, heating, vibration, UV radiation, DUV radiation, sound waves, microwaves, magnetism, MASER (Microwave Amplification by Simulated Emission of Radiation), SASER (Sound Amplification by Simulated Emission of Radiation), electric current, electrical arc, heat, cooling, deuterium oxide (D 2 O), semi-heavy water (HDO), hydrogen peroxide (H 2 O 2 ), glycol or combinations thereof to the substrate. 
     
     
         4 . The method of  claim 1 , wherein the substrate comprises ice or dry ice. 
     
     
         5 . The method of  claim 1 , wherein the substrate comprises a solid surface, wherein the solid surface is coated at least in part with liquid water (H 2 O), deuterium oxide (D 2 O), semi-heavy water (HDO), hydrogen peroxide (H 2 O 2 ) or combinations thereof. 
     
     
         6 . The method of  claim 5 , wherein the solid surface comprises silicon, copper, nickel, cobalt, boron, iron, gold, silver, aluminum, germanium, boron nitride, glass, ceramic, biomimetic membrane, silicon dioxide, silica, aluminum silicate, fused silica, silicon carbide, plastics, polymers, resins, epoxy, titanium, concrete, steel, asphalt, cement, nylon, graphite, diamond, amorphous carbon, h-BN, Si 3 N 4 , poly(2-phenylpropyl)methysiloxane (PPMS), poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(acrylonitrile-co-butadiene-co-styrene) (AB). 
     
     
         7 . The method of  claim 1 , wherein the substrate comprises a solid surface, wherein the solid surface is coated at least in part with ice. 
     
     
         8 . The method of  claim 1 , wherein the hydrothermal heating comprises heating the reaction chamber by application of a flame, an electric heating element, an electrical arc discharge or combinations thereof. 
     
     
         9 . The method of  claim 8 , wherein the reaction chamber comprises a non-inertial cavitation-inducing reactor. 
     
     
         10 . The method of  claim 9 , wherein the non-inertial cavitation-inducing reactor comprises an external energy input comprising ultrasound waves, acoustic levitation waves, pulsed laser light, radio frequency (RF) emissions, electromagnetic emissions, MASER, SASER or combinations thereof. 
     
     
         11 . The method of  claim 9 , wherein the reactor chamber comprises an inertial cavitation-inducing reactor. 
     
     
         12 . The method of  claim 11 , wherein the inertial cavitation-inducing reactor comprises a flow restricting venturi-type element, wherein the flow restricting venturi-type element comprises a curved venturi channel designed to induce cyclonic flow. 
     
     
         13 . The method of  claim 1 , wherein heating the carbonaceous material comprises pyrolysis. 
     
     
         14 . The method of  claim 1 , wherein heating the carbonaceous material comprises an oxidation/reduction chemical reaction. 
     
     
         15 . The method of  claim 14 , wherein the oxidation/reduction chemical reaction comprises dehydration of the carbonaceous material. 
     
     
         16 . The method of  claim 15 , wherein the dehydrated carbonaceous material comprises sugar. 
     
     
         17 . The method of  claim 1 , wherein the reaction chamber comprises an autoclave. 
     
     
         18 . The method of  claim 1 , wherein the synthesis gas species comprise under carbon monoxide, nascent hydrogen ions, ionic methane precursor gases and combinations thereof. 
     
     
         19 . A method of graphene oxide synthesis, comprising:
 (a) creation of synthesis gas species in the presence of an oxidizing agent from the hydrothermal heating of a carbonaceous material in a reaction chamber;   (b) collection, direction and removal of the resulting vapors from the reaction chamber to a substrate; and   (c) deposition of graphene oxide on the surface of the substrate.   
     
     
         20 . The method of  claim 19 , further comprising application of sonication, ultrasonication, surfactant, oxidizing agents, reducing agents, ionizing irradiation, pH adjustment, pressurization, depressurization, heating, vibration, UV radiation, DUV radiation, sound waves, microwaves, magnetism, MASER (Microwave Amplification by Simulated Emission of Radiation), SASER (Sound Amplification by Simulated Emission of Radiation), electric current, electrical arc, heat, cooling, deuterium oxide (D 2 O), semi-heavy water (HDO), hydrogen peroxide (H 2 O 2 ), glycol or combinations thereof to the substrate. 
     
     
         21 . A method of graphene synthesis, comprising:
 (a) creation of synthesis gas species from the hydrothermal heating of a carbonaceous material in a reaction chamber; and   (b) collection, direction and removal of the resulting vapors from the reaction chamber to a substrate.   
     
     
         22 . The method of  claim 21 , wherein the substrate comprises water, wherein the method further comprises application of sonication, ultrasonication, surfactant, oxidizing agents, reducing agents, ionizing irradiation, pH adjustment, pressurization, depressurization, heating, vibration, UV radiation, DUV radiation, sound waves, microwaves, magnetism, MASER (Microwave Amplification by Simulated Emission of Radiation), SASER (Sound Amplification by Simulated Emission of Radiation), electric current, electrical arc, heat, cooling, deuterium oxide (D 2 O), semi-heavy water (HDO), hydrogen peroxide (H 2 O 2 ), glycol or combinations thereof to the substrate. 
     
     
         23 . A method of graphene oxide synthesis, comprising:
 (a) creation of synthesis gas species in the presence of an oxidizing agent from the hydrothermal heating of a carbonaceous material in a reaction chamber; and   (b) collection, direction and removal of the resulting vapors from the reaction chamber to a substrate.   
     
     
         24 . The method of  claim 23 , wherein the substrate comprises water, wherein the method further comprises application of sonication, ultrasonication, surfactant, oxidizing agents, reducing agents, ionizing irradiation, pH adjustment, pressurization, depressurization, heating, vibration, UV radiation, DUV radiation, sound waves, microwaves, magnetism, MASER (Microwave Amplification by Simulated Emission of Radiation), SASER (Sound Amplification by Simulated Emission of Radiation), electric current, electrical arc, heat, cooling, deuterium oxide (D 2 O), semi-heavy water (HDO), hydrogen peroxide (H 2 O 2 ), glycol or combinations thereof to the substrate. 
     
     
         25 . A method of graphene synthesis, comprising:
 (a) application of a carbonaceous vapor containing C 1  to C 5  radicals to an aqueous solution; and   (b) recovery of graphene from the surface of the aqueous solution.   
     
     
         26 . The method of  claim 25 , further comprising application of sonication, ultrasonication, surfactant, oxidizing agents, reducing agents, ionizing irradiation, pH adjustment, pressurization, depressurization, heating, vibration, UV radiation, DUV radiation, sound waves, microwaves, magnetism, MASER (Microwave Amplification by Simulated Emission of Radiation), SASER (Sound Amplification by Simulated Emission of Radiation), electric current, electrical arc, heat, cooling, deuterium oxide (D 2 O), semi-heavy water (HDO), hydrogen peroxide (H 2 O 2 ), glycol or combinations thereof to the aqueous solution. 
     
     
         27 . A method of graphene oxide synthesis, comprising:
 (a) application of a carbonaceous vapor containing C 1  to C 5  radicals to an aqueous solution; and   (b) recovery of graphene oxide from surface of the aqueous solution.   
     
     
         28 . The method of  claim 27 , further comprising application of sonication, ultrasonication, surfactant, oxidizing agents, reducing agents, ionizing irradiation, pH adjustment, pressurization, depressurization, heating, vibration, UV radiation, DUV radiation, sound waves, microwaves, magnetism, MASER (Microwave Amplification by Simulated Emission of Radiation), SASER (Sound Amplification by Simulated Emission of Radiation), electric current, electrical arc, heat, cooling, deuterium oxide (D 2 O), semi-heavy water (HDO), hydrogen peroxide (H 2 O 2 ), glycol or combinations thereof to the aqueous solution. 
     
     
         29 . A method of graphene hydrogel synthesis, comprising:
 (a) application of a carbonaceous vapor containing C 1  to C 5  radicals to an aqueous solution; and   (b) recovery of a graphene hydrogel layer from the aqueous solution.   
     
     
         30 . The method of  claim 29 , further comprising application of sonication, ultrasonication, surfactant, oxidizing agents, reducing agents, ionizing irradiation, pH adjustment, pressurization, depressurization, heating, vibration, UV radiation, DUV radiation, sound waves, microwaves, magnetism, MASER (Microwave Amplification by Simulated Emission of Radiation), SASER (Sound Amplification by Simulated Emission of Radiation), electric current, electrical arc, heat, cooling, deuterium oxide (D 2 O), semi-heavy water (HDO), hydrogen peroxide (H 2 O 2 ), glycol or combinations thereof to the aqueous solution. 
     
     
         31 . A method of graphene oxide hydrogel synthesis, comprising:
 (a) application of a carbonaceous vapor containing C 1  to C 5  radicals to an aqueous solution; and   (b) recovery of a graphene oxide hydrogel layer from the aqueous solution.   
     
     
         32 . The method of  claim 31 , further comprising application of sonication, ultrasonication, surfactant, oxidizing agents, reducing agents, ionizing irradiation, pH adjustment, pressurization, depressurization, heating, vibration, UV radiation, DUV radiation, sound waves, microwaves, magnetism, MASER (Microwave Amplification by Simulated Emission of Radiation), SASER (Sound Amplification by Simulated Emission of Radiation), electric current, electrical arc, heat, cooling, deuterium oxide (D 2 O), semi-heavy water (HDO), hydrogen peroxide (H 2 O 2 ), glycol or combinations thereof to the aqueous solution. 
     
     
         33 . A method of composite fabrication, comprising:
 (a) application of a graphene hydrogel produced according to the method of  claim 29 , to a liquid composite mixture prior to its curing into a solid; and   (b) curing the composite mixture into a solid.   
     
     
         34 . A method of composite fabrication, comprising:
 (a) application of a graphene oxide hydrogel produced according to the method of  claim 31 , to a liquid composite mixture prior to its curing into a solid; and   (b) curing the composite mixture into a solid.   
     
     
         35 . A method of graphene synthesis, comprising:
 (a) application of a cyclic-carbon containing aqueous solution to coat a substrate that is sufficient to withstand the heat of pyrolysis of the aqueous solution;   (b) pyrolysis of the aqueous solution coating on the substrate under conditions to produce graphene; and   (c) recovery of graphene from the surface of the substrate.   
     
     
         36 . A method of surface graphitized abrasive nanoparticle synthesis, comprising:
 (a) ball milling of a carbonaceous material in the presence of a solvent to create a slurry;   (b) addition of a metal oxide powder or a nano-powder to the slurry; and   (c) recovery of surface graphitized abrasive nanoparticles from the slurry.   
     
     
         37 . The method of  claim 36 , wherein the carbonaceous material comprises solid CO 2  (dry ice), bituminous coal, peat, lignite, sub-bituminous coal, pulverized coal, nano-coal, steam coal, cannel coal, anthracite, charcoal, carbon black, activated charcoal, “activated nano-coal”, sugar char and combinations thereof. 
     
     
         38 . The method of  claim 36 , wherein the solvent comprises cyclohexane, toluene, polyphenol, benzaldehyde, benzotriazole, benzyl 1-naphthyl carbonate, benzene, ethyl benzene, styrene, benzonitrile, phenol, phthalic anhydride, phthalic acid, terephthalic acid, p-toluic acid, benzoic acid, aminobenzoic acid, benzyl chloride, isoindole, ethyl phthalyl ethyl glycolate, N-phenyl benzamine, methoxybenzoquinone, benzylacetone, benzylideneacetone, hexyl cinnamaldehyde, 4-amino-2-hydroxytoluene, 3-aminophenol, a benzoate, terpene, ethanol, methanol, isopropanol, isobutane, cyclobutane, pentane, isopentane, neopentane, cyclopentane, hexane, octane, kerosene, an ester, a ketone, an aldehyde, an ether or combinations thereof.