Solvent-based methods for production of graphene nanoribbons

Abstract

Embodiments of the present invention provide methods of preparing functionalized graphene nanoribbons by (1) exposing a plurality of carbon nanotubes to an alkali metal source in the presence of an aprotic solvent, wherein the exposing opens the carbon nanotubes; and (2) exposing the opened carbon nanotubes to an electrophile to form functionalized graphene nanoribbons. Such methods may also include a step of exposing the opened carbon nanotubes to a protic solvent in order to quench any reactive species on the opened carbon nanotubes. Further embodiments of the present invention pertain to graphene nanoribbons formed by the methods of the present invention. Additional embodiments of the present invention pertain to nanocomposites and fibers containing the aforementioned graphene nanoribbons.

What is claimed is: 
     
         1 . A method of preparing functionalized graphene nanoribbons, wherein the method comprises:
 exposing a plurality of carbon nanotubes to an alkali metal source in the presence of an aprotic solvent, wherein the exposing opens the carbon nanotubes; and   exposing the opened carbon nanotubes to an electrophile to form functionalized graphene nanoribbons.   
     
     
         2 . The method of  claim 1 , further comprising a step of exposing the opened carbon nanotubes to a protic solvent. 
     
     
         3 . The method of  claim 2 , wherein the protic solvent is selected from the group consisting of formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water, hydrochloric acid, sulfuric acid, ammonia, diethyl amine, dialkylamines, monoalkylamines, diarylamines, monoarylamines, monoalkymonoarylamines, and combinations thereof. 
     
     
         4 . The method of  claim 1 , wherein the carbon nanotubes are opened parallel to their longitudinal axis. 
     
     
         5 . The method of  claim 1 , wherein the method takes place at room temperature. 
     
     
         6 . The method of  claim 1 , wherein the carbon nanotubes are selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, triple-walled carbon nanotubes, multi-walled carbon nanotubes, ultra-short carbon nanotubes, and combinations thereof. 
     
     
         7 . The method of  claim 1 , wherein the carbon nanotubes comprise multi-walled carbon nanotubes. 
     
     
         8 . The method of  claim 1 , wherein the alkali metal source is selected from the group consisting of lithium, potassium, sodium, rubidium, caesium, alloys thereof, and combinations thereof. 
     
     
         9 . The method of  claim 1 , wherein the alkali metal source comprises potassium. 
     
     
         10 . The method of  claim 1 , wherein the aprotic solvent is selected from the group consisting of diethyl ether, tetrahydrofuran, 1,4-dioxane, glyme, 1,2-dimethoxyethane, diglyme, tetraglyme, amines, N,N,N′,N′-tetramethylethylenediamine, triethylamine, 1,4-diazabicyclo[2.2.2]octane, trialkylamines, dialkylarylamines, alkyldiarylamines, dimethylformamide, and combinations thereof. 
     
     
         11 . The method of  claim 1 , wherein the electrophile is selected from the group consisting of water, alcohols, organic halides, alkenes, alkyl halides, acyl halides, allylic halides, benzyl halides, benzylic halides, alkenyl halides, aryl halides, alkynyl halides, fluoralkly halides, perfluoroalkyl halides, aldehydes, ketones, methyl vinyl ketones, esters, sulfonate esters, acids, acid chlorides, carboxylic acids, carboxylic esters, carboxylic acid chlorides, carboxylic acid anhydrides, carbonyl bearing compounds, enones, nitriles, carbon dioxide, halogens, monomers, vinyl monomers, ring-opening monomers, isoprenes, butadienes, styrenes, acrylonitriles, methyl vinyl ketones, methacrylates, 1,4-dimethoxy-2-vinylbenzene, methyl methacrylate, alkyl acrylates, alkyl methacrylates, trimethylsilyl chlorides, tert-butyldimethylsilyl chlorides, triphenylsilyl chlorides, epoxides, carbon dioxide, carbon disulfide, tert-butanol, 2-methylpropene, bromine, chlorine, iodine, fluorine, and combinations thereof. 
     
     
         12 . The method of  claim 1 , wherein the electrophile comprises carbon dioxide. 
     
     
         13 . The method of  claim 1 , wherein the electrophile is a monomer. 
     
     
         14 . The method of  claim 13 , wherein the monomer is selected from the group consisting of olefins, vinyl monomers, styrenes, isoprenes, butadienes, acrylonitriles, methyl vinyl ketones, alkyl acrylates, alkyl methacrylates, ring opening monomers, epoxides, and combinations thereof. 
     
     
         15 . The method of  claim 13 , wherein the monomer polymerizes upon addition to the opened carbon nanotubes, thereby forming polymer-functionalized graphene nanoribbons. 
     
     
         16 . The method of  claim 1 , wherein the formed graphene nanoribbons comprise edge-functionalized graphene nanoribbons. 
     
     
         17 . The method of  claim 1 , wherein the formed graphene nanoribbons have a conductivity ranging from about 0.1 S/cm to about 9,000 S/cm. 
     
     
         18 . The method of  claim 1 , further comprising a step of deintercalating functional groups from one or more layers of graphene nanoribbons. 
     
     
         19 . The method of  claim 18 , wherein the deintercalating occurs by heating the formed graphene nanoribbons. 
     
     
         20 . The method of  claim 1 , further comprising a step of exfoliating one or more layers of graphene from the formed graphene nanoribbons. 
     
     
         21 . The method of  claim 20 , wherein the exfoliating comprises exposure of the graphene nanoribbons to a gas, wherein the gas is selected from the group consisting of carbon dioxide, nitrogen gas, hydrogen gas, hydrogen chloride, air, and combinations thereof. 
     
     
         22 . A composite comprising graphene nanoribbons, wherein the graphene nanoribbons are edge-functionalized. 
     
     
         23 . The composite of  claim 22 , wherein the graphene nanorribons contain unfunctionalized basal planes. 
     
     
         24 . The composite of  claim 22 , wherein the graphene nanoribbons are edge-functionalized with polymers. 
     
     
         25 . The composite of  claim 24 , wherein the polymers are selected from the group consisting of polystyrenes, polyisoprenes, polybutadienes, polyacrylonitriles, polymethyl vinyl ketones, poly alkyl acrylates, polyalkyl methacrylates, polyols, and combinations thereof. 
     
     
         26 . The composite of  claim 22 , wherein the graphene nanoribbons are edge-functionalized with functional groups selected from the group consisting of alkyl groups, acyl groups, allylic groups, benzyl groups, benzylic groups, alkenyl groups, aryl groups, alkynyl groups, aldehydes, ketones, esters, carboxyl groups, carbonyl groups, halogens, and combinations thereof. 
     
     
         27 . The composite of  claim 22 , wherein the edge-functionalized graphene nanorribons comprise at least one of alkyl-functionalized graphene nanoribbons, hexadecylated graphene nanoribbons, octylated graphene nanoribbons, butylated graphene nanoribbons, and combinations thereof. 
     
     
         28 . The composite of  claim 22 , wherein the composites are utilized as components of at least one of transparent conductive displays, de-icing circuits, gas barrier composites, screens, and combinations thereof. 
     
     
         29 . A fiber comprising graphene nanoribbons, wherein the graphene nanoribbons are edge-functionalized. 
     
     
         30 . The fiber of  claim 29 , wherein the graphene nanorribons contain unfunctionalized basal planes. 
     
     
         31 . The fiber of  claim 29 , wherein the graphene nanoribbons are edge-functionalized with polymers. 
     
     
         32 . The fiber of  claim 29 , wherein the polymers are selected from the group consisting of polystyrenes, polyisoprenes, polybutadienes, polyacrylonitriles, polymethyl vinyl ketones, poly alkyl acrylates, polyalkyl methacrylates, polyols, and combinations thereof. 
     
     
         33 . The fiber of  claim 29 , wherein the graphene nanoribbons are edge-functionalized with functional groups selected from the group consisting of alkyl groups, acyl groups, allylic groups, benzyl groups, benzylic groups, alkenyl groups, aryl groups, alkynyl groups, aldehydes, ketones, esters, carboxyl groups, carbonyl groups, halogens, and combinations thereof. 
     
     
         34 . The fiber of  claim 29 , wherein the edge-functionalized graphene nanorribons comprise at least one of alkyl-functionalized graphene nanoribbons, hexadecylated graphene nanoribbons, octylated graphene nanoribbons, butylated graphene nanoribbons, and combinations thereof. 
     
     
         35 . The fiber of  claim 29 , wherein the fibers are utilized as components of at least one of transparent conductive displays, de-icing circuits, gas barrier fibers, screens, and combinations thereof.