WO2020243345A1 - Monodispersed nanocarbons prepared from polysulfonated nanopolymers - Google Patents

Abstract

Spherical carbon nanoparticles having diameters in the range from about 200 to about 900 nm and methods of making the same. According the methods provided herein, spherical nanopolymers are formed through a miniemulsion process, the spherical nanopolymers are polysulfonated then pyrolyzed to form spherical carbon nanoparticles. The surfaces may be further modified with, e.g., various adsorbents to further modify the properties. The formation process allows production of various pore structures, from non-porous to fully porous, with the tunability of pore structure allowing micropores, mesopores, macropores, and combinations of any of the foregoing, allowing for a wide range of surface areas making these nanocarbons suitable for many applications, including sample and bulk preparation, purification, and analysis, and drug delivery applications.

Description

MON ODISPERSED NANOCARBONS PREPARED FROM

POLYSULFONATED NANOPOLYMERS

[0001] Cross-Reference to Related Applications

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application No. 62/855,112, filed May 31, 2019, the entirety of which is incorporated herein by reference.

[0003] Carbon adsorbents have long been important in many diverse applications, ranging from bulk-scale solution process devices, to analytical devices, to energy storage.

[0004] Conventional methods for producing high purity carbon adsorbents include those disclosed in US Patents No. 4,839,331. 4,957,897, 5,094,754, 5,021,391 and 5,104,530. This series of patents disclose a process for preparing carbon molecular sieves by forming a polymeric resin, polysulfonating the resin, and then pyrolyzing the polysulfonated resin. Because of the high quality of materials produced, these methods are useful for producing high quality carbon down to micron-size scale.

[0005] Smaller particles— on the nano-size scale— are highly desired for many applications such as filtration media, electrical devices and coatings, as well as others. Conventional methods, however, cannot produce carbon nanospheres. A need exists for new methods that can be used to produce nanocarbon materials. Such new method should allow for high purity, control over particle size, and control over porosity.

[0006] Summary [0007] Provided herein are new carbon nanosphere particles. These carbon nanosphere particles, or carbon nanospheres, preferably contain greater than 90% carbon by weight and have a diameter in the range from about 10 nm to 900 nm. In certain embodiments, the carbon nanospheres are monodisperse, while in other embodiments the carbon nanospheres are polydisperse. In some embodiments, the carbon nanospheres include a plurality of pores, which may include micropores, mesopores, macropores or a combination of any two or three types of pores. In some embodiments, the carbon nanospheres may be nonporous. In further embodiments, the carbon nanospheres may include an external graphitic layer. In still further embodiments, the carbon nanospheres may also include an adsorptive coating.

[0008] Also provided are methods for preparing spherical nanocarbons, the method comprising the steps of forming a spherical nanopolymer through a miniemulsion process; polysulfonating the spherical nanopolymer to form a polysulfonated spherical nanopolymer; drying the polysulfonated spherical nanopolymer; pyrolyzing the polysulfonated spherical nanopolymer to yield a spherical nanocarbon, and optionally, activating the spherical nanocarbon. In some embodiments, the spherical nanocarbon is graphitized by thermally treating the spherical nanocarbon at a temperature of at least 2500°C.

[0009] In a preferred embodiment, the mini emulsion process includes preparing a dual phase mixture having an aqueous phase having an aqueous solvent, a water-soluble initiator and a surfactant wherein the concentration of surfactant is below the critical micelle concentration for the surfactant; and an organic phase having a vinylaromatic monomer, a co-stabilizer and, if forming porous nanocarbons, a porogen; applying sufficient shear to the dual phase mixture to form an emulsion; and heating the emulsion to about 70°C with shear mixing until the polymerization reaction is complete, yielding the spherical

nanopolymer. [0010] Also provided are devices including the spherical nanoparticles disclosed herein.

[0011] Brief Description of the Figures

[0012] Figure 1 provides a schematic of the miniemulsion process disclosed herein.

[0013] Figure 2 provides a mathematical example of a Gaussian distribution graph.

[0014] Figure 3 shows the particle size distribution for monodisperse carbon nanospheres prepared at 227 nm.

[0015] Figure 4 shows an exemplary particle size distribution curve for a

monodisperse carbon microsphere.

[0016] Figure 5 illustrates the pore structure of a porous carbon nanosphere as described herein.

[0017] Figure 6 shows Van Deemter Plots for carbon microspheres with various pore structures.

[0018] Figure 7 is a drawing illustrating velocity changes in pores.

[0019] Figure 8 is a plot of incremental pore volume (cc/g) versus pore diameter (A) for the starting polymer materials for two carbon microspheres made using a standard emulsion process compared with starting polymer materials for two carbon nanospheres made using the miniemulsion process described herein.

[0020] Figure 9 shows the pore structure of a spherical nanopolymer (before pyrolysis) and the resulting spherical nanocarbon (after pyrolysis).

[0021] Figure 10 is an SEM image of graphitized, spherical nanocarbon hybrid. [0022] Figure 11 shows a DFT overlay plot for an uncoated spherical nanocarbon (solid) and for the same spherical nanocarbon after applying a polymer coating (dashed line).

[0023] Detailed Description

[0024] Provided herein are new methods for the production of carbon

nanospheres. The new methods provided herein not only allow production of spherical carbons with diameters in the nanometer range, and the ability to control porosity.

[0025] The inventors have found that in order to achieve particles on the scale of nanometers, the way in which the nanoparticles are produced is limited. For nanocarbons disclosed herein, a miniemulsion technique is utilized. The miniemulsion process is illustrated schematically in Figure 1. This method of polymerization has some similarities to emulsion polymerization. In this technique, there are two phases: 1) aqueous and 2) organic. The aqueous phase is usually made up of water, a water-soluble initiator and a surfactant. The organic phase contains the monomer(s) and co-stabilizer and optionally porogens. These two immiscible phases are mixed together by shear through the use of a rotor stator or ultrasonication. The high shear allows for stability of droplets within a continuous phase. A stark difference from emulsion polymerization is that the surfactant in the miniemulsion process is always added below the critical micelle concentration (CMC), which means that the mechanism of particle formation is no longer by micellar nucleation, but by droplet nucleation. A further difference is the use of a co-stabilizer, which is added to prevent Ostwald ripening or coalescence of smaller particles that merge together to create larger particles.

[0026] As used herein the terms carbon nanospheres, carbon nanosphere particles, carbon nanoparticles, spherical nanocarbons, and nanocarbons are used interchangeably to refer to approximately spherical particles composed primarily of carbon and having a diameter of less than 1 micron, or more specifically, a diameter in the range from about 1 nm up to 1 micron. In some embodiments described herein, the carbon nanospheres have a diameter in the range from about 10 nm to about 900 nm. In other embodiments, the carbon nanospheres have a diameter in the range from about 200 nm to about 800 nm.

In other embodiments, the carbon nanospheres have a diameter in the range from about 150 nm to about 325 nm. In various embodiments, the carbon nanospheres may have a diameter of 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm or 900 nm. In some embodiments, the carbon nanospheres fall within a specified range. In addition to the preferred diameter ranges specified above, other preferred ranges include, e.g., from about 250 nm to about 750 nm, from about 300 nm to about 700 nm, from about 350 nm to about 650 nm, from about 300 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, from about 200 nm to about 600 nm, from about 200 nm to about 700 nm, from about 200 nm to about 900 nm, from about 300 nm to about 400 nm, from about 300 nm to about 500 nm, from about 300 nm to about 600 nm, from about 300 nm to about 700 nm, from about 300 nm to about 800 nm, from about 300 nm to about 900 nm, from about 400 nm to about 500 nm, from about 400 nm to about 600 nm, from about 400 nm to about 700 nm, from about 400 nm to about 800 nm, from about 400 nm to about 900 nm, from about 500 nm to about 600 nm, from about 500 nm to about 700 nm, from about 500 nm to about 800 nm, from about 500 nm to about 900 nm, from about 600 nm to about 700 nm, from about 600 nm to about 800 nm, from about 600 nm to about 900 nm, from about 700 nm to about 800 nm, from about 700 nm to about 900 nm, and from about 800 nm to about 900 nm.

[0027] Methods and instruments are known for measuring particle size. It is noted that nanospheres, like particles, have a distribution of particle size diameters within any sample. Accordingly, when referring to specific particle sizes, it is understood that the inventors are referring to a distribution of particle sizes, which can be quite narrow, i.e., monodisperse, or broader, i.e., polydisperse.

[0028] Dispersivity can be measured by a number of methods. One exemplary method of measuring particle size is using a laser scattering instrument. Using this method, the mean particle size and standard deviation are calculated.

Particles are monodisperse when the standard deviation of particle size is below about 6%; preferably, the standard deviation of particle sizes is below 6.0%.

[0029] In a second exemplary method, particle size distribution of a plurality of particles, such as the carbon nanospheres described herein, may be measured using an electrical zone sensing particle analyzer. The mean particle size is determined, and standard deviation calculated. From Figure 2, Dio and D90 are ± 2 standard deviations, respectively. Dispersivity is calculated as D (90/10), or the particle size value at D90 (+2 standard deviations) divided by Dio (-2 standard deviations). Using this method, D (90/10) values below about 1.2, preferably below about 1.17, are considered monodisperse.

[0030] Advantageously, using the methods provided herein, the synthesis of the carbon nanospheres can be tailored to produce either monodisperse or polydisperse particles without the need for any particle size sorting.

[0031] Figure 3 shows a particle distribution graph for carbon nanospheres prepared at 227 nm, illustrating that the particles are monodisperse as prepared, even through the carbonization process. A laser scatter instrument was used to measure the particle size distribution. Figure 4, for comparison shows the particle size distribution for a carbon microsphere (2.5 pm diameter) prepared using a conventional emulsion process. Figures 3 and 4 illustrate that both the inventive carbon nanospheres and the conventional carbon microspheres are monodisperse.

[0032] The carbon nanospheres described herein typically are about 99% carbon and about 1% hydrogen by weight. In some embodiments, however, the carbon nanospheres may contain about 80% carbon by weight. More preferably, the carbon nanospheres are at least about 90% carbon by weight. In some embodiments, the carbon nanospheres are at least about 95% carbon by weight. In other embodiments, the carbon nanospheres are at least about 97% carbon by weight. When the percentage of carbon, by weight, is at the lower end of the preferred range, e.g. around 80% carbon by weight, the overall weight may be affected by, e.g., the addition of oxygen during preparation. For various applications, it may be desirable to have a higher or lower percentage of carbon by weight. For example, in various embodiments, the carbon nanospheres may contain about 80%, about 82%, about 85%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, or about 99% carbon, by weight.

[0033] The carbon atoms of the carbon nanospheres described herein may be arranged in sheet-like complexes of interconnected 6-carbon rings, and each 6- carbon ring may include from one and three double bonds from adjacent carbon atoms. The surface of the carbon nanospheres may include carbon atoms that possess predominantly sp³ orbitals, likely due to the extensive double bonding from adjacent carbon atoms. The surface of the carbon microspheres may be relatively hydrophobic as a result of this structure.

[0034] The carbon nanospheres described herein typically have a surface area in the range from about 1 m²/g to about 4000 m²/g of carbon nanosphere particles. In certain embodiments, the surface area of the carbon nanospheres is in the range from about 300 to about 3500 m²/g. In some embodiments, the surface area of the carbon nanospheres is in the range from about 1500 to about 2500 m²/g. In other embodiments, the surface area of the carbon nanospheres is in the range from about 2000 to about 3500 m²/g. In some particularly preferred embodiments, the surface area of the carbon nanospheres is in the range from about 500 m²/g to about 1000 m²/g. For various applications, other surface area ranges may be preferred. Some exemplary surface area ranges include, e.g., from about 1 m²/g to about 100 m²/g, from about 1 m²/g to about 200 m²/g, from about 1 m²/g to about 300 m²/g, from about 1 m²/g to about 400 m²/g, from about 100 m²/g to about 4000 m²/g, from about 500 m²/g to about 4000 m²/g, from about 1000 m²/g to about 4000 m²/g, from about 2000 m²/g to about 4000 m²/g, from about 300 m²/g to about 3000 m²/g, from about 500 m²/g to about 3000 m²/g, from about 1000 m²/g to about 3000 m²/g, and from about 2000 m²/g to about 3000 m²/g.

[0035] In some embodiments, the carbon nanospheres described herein are porous, i.e., there is a defined pore structure in the particle. In other

embodiments, the carbon nanospheres may be non-porous. The presence or absence of pores, and the pore structure itself, can be modified in accordance with the methods described herein.

[0036] A pore can be defined as any cavity present on a solid surface with a depth:width ratio of approximately 10: 1. The carbon nanospheres described herein may have open pores, i.e., pores open to the particle surface and are accessible to an external fluid. Open pores may be open at both ends or only one end, e.g., blind or dead end. Alternately, in other embodiments, the carbon nanospheres may include pores that are not accessible from the surface because they are only in the interior (not available to external fluids but affect, e.g., density, mechanical strength, etc.)

[0037] In various embodiments, the carbon nanospheres described herein can have open pore structures, closed pore structures, or a combination of open pore structures and closed pore structures.

[0038] Pores in particulate materials are typically categorized by diameter.

Macropores have a >500 A (50 nm) diameter, mesopores have a 20-500 A (2- 50 nm) diameter, and micropores have a <20 A (2 nm) diameter. Figure 5 provides an illustration of macropores, mesopores, and micropores in a spherical carbon particle. [0039] In some embodiments, the pores are selected from micropores, mesopores, macropores, and combinations thereof. In some embodiments, the carbon nanospheres have primarily micropores. In other embodiments, the carbon nanospheres have primarily mesopores. In still other embodiments, the carbon nanospheres have primarily macropores.

[0040] The carbon nanospheres may have a latticework that forms a plurality of interconnected pores. Typically, in such embodiments, the carbon nanospheres may include micropores having mean pore diameters greater than about 10 A located predominantly near the exposed exterior surface of the carbon nanosphere. Ultramicropores having mean internal diameters less than about 7 A may be located within the walls of the interconnected micropores in the interior of the carbon nanosphere. Aspects of the fabrication process, such as those described below, may control the distribution of pore sizes.

[0041] In some embodiments, the carbon nanospheres include a combination of micropores, mesopores and macropores. Moreover, because the methods described herein allow for production of carbon nanoparticles with greatly varying pore structures, from non-porous to fully porous with varying pore sizes, the potential ratios of micropore:mesopore:macropore are (100:0:0) to (0:100:0) to (0:0: 100). In some embodiments, the pore structures further contain ultramicropores.

[0042] In a preferred embodiment, the carbon nanospheres include a combination of micropores and macropores. In this embodiment, the ratio of micropores to macropores is in the range from about 1% to about 99%. In some further embodiments, the pore structures further contain ultramicropores.

[0043] Controlling pore composition is important as it determines the adsorption and desorption characteristics of the particle. Different pore structures are desirable for different applications. A highly microporous carbon which possesses mesopores and/or macropores is kinetically improved compared to a microporous-only carbon. A mesoporous-only carbon is best for large- biomolecule adsorption and chromatographic processes.

[0044] Figure 6 shows Van Deemter plots for carbon microspheres; this is illustrative for the carbon nanospheres described herein which can be produced with similar pore structures. Figure 7 provides a graphical illustration of the velocity changes in pores. In Figure 7, vi is the interparticle velocity as well as the macropore velocity. V2 is the mesopore velocity, approximately 0.1 vi. V3 is the micropore velocity, approximately 0.01-0.001 vi. Velocity and diffusion are synonymous here.

[0045] Figure 8 shows a plot of incremental pore volume (cc/g) versus pore diameter (A) for the starting polymer materials for two carbon microspheres made using a standard emulsion process compared with starting polymer materials for two carbon nanospheres made using the miniemulsion process described herein.

[0046] Figure 9 illustrates the pores present in the mesopore and macropore ranges are maintained through the polysulfonation process. It is typical to observe some coalescing of these larger pores to produce micropores during the carbonization once the skeletal framework is stabilized by the polysulfonation process. The carbon yield is approximately 90-95%. As a comparison, without the polysulfonation step, the carbon yield is approximately 5%, and no porosity is maintained.

[0047] In some embodiments, the carbon nanospheres include an external layer of graphitic carbon. Carbonization, by heating the pyrolyzed or

pyrolyzed/activated carbon nanospheres to a temperature of at least 2500°C, results in graphitized, spherical polymer carbon nanospheres. These carbon nanospheres possess an external layering of graphitic carbon with an amorphous internal carbon structure. This layer is typically 2% of the total carbon mass.

The graphitic/amorphous hybrid carbon is stable at high pressure of approximately 10,000 psi and does not fracture during vibration. Figure 10 is a low-resolution SEM image of a graphitized, spherical polymer carbon.

[0048] In still other embodiments, the carbon nanospheres may include an absorptive coating bonded to the surface of the carbon nanospheres. In one embodiment, the absorptive coating may be an HLB polymeric coating, such as that disclosed in International Patent Publication No. WO2019040868, incorporated herein by reference. In other embodiments, the polymeric coating may be polyethylene glycol, or any non-polar to polar polymeric stationary phase used for gas chromatography (GC) or solid phase extraction (SPE) applications. Some exemplary polymeric coatings are included in the table below.

[0049] Further provided are methods of producing the spherical nanocarbons provided herein.

[0050] In a first method for producing porous spherical nanocarbon, the method includes the steps of first forming a porous spherical nanopolymer through a miniemulsion process; polysulfonating the porous spherical nanopolymer to form a polysulfonated porous spherical nanopolymer; drying the polysulfonated porous spherical nanopolymer; pyrolyzing the polysulfonated porous spherical nanopolymer to yield a porous spherical nanocarbon, and optionally, activating the porous spherical nanocarbon.

[0051] The miniemulsion polymerization involves the combination of a

continuous phase and a dispersed phase. The continuous phase (aqueous phase) is made up of an aqueous solvent, water-soluble initiator, and surfactant. The dispersed phase (organic phase) contains the monomer, costabilizer and, optionally, porogens. The two phases are mixed together via homogenization while stirring with an overhead stirrer. Once sufficiently mixed, the mixture is heated to 70°C with stirring for a time sufficient to form polymer nanospheres.

[0052] The water-soluble initiator may be a thermal initiator or a redox initiator. Some exemplary thermal initiators selected from ammonium persulfate, potassium persulfate, lauroyl peroxide, benzoyl peroxide, 2,2- azobisisobutyronitrile and combinations thereof. Some exemplary redox initiators include ammonium persulfate/sodium sulfite, ammonium

persulfate/tetram ethyl ethylene diamine, hydrogen peroxide/sodium

formaldehyde sulfoxylate and combinations thereof. Other suitable initiators may be used as well.

[0053] The surfactant used in the miniemulsion process may be an anionic surfactant, a cationic surfactant, or a nonionic surfactant. Some exemplary anionic surfactants for use in the methods described herein include sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, potassium oleate and combinations thereof. Some exemplary cationic surfactants

cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, octadecyl pyridium bromide and combinations thereof. Some exemplary nonionic surfactants polyethylene oxide derivatives, and nonylphenol polyethoxylate with an average of 40 ethylene oxide units. Other suitable surfactants may also be used.

[0054] Importantly, in the mini-emulsion process and in contrast to suspension polymerization processes, the surfactant is always added at a concentration below the critical micelle concentration (CMC). Addition of the surfactant below the CMC means that the mechanism of particle formation is no longer by micellar nucleation, but by droplet nucleation.

[0055] The dispersed phase, as noted above, contains the monomer, costabilizer and porogens. In a preferred embodiment, the monomer is a vinylaromatic monomer. Suitable vinylaromatic monomer include, but are not limited to, divinylbenzene, styrene, alpha-methylstyrene, vinyltoluene, p-methyl styrene, ethyl-vinylbenzene, vinylnaphthalene, trivinylbenzene,

vinylisopropenylbenzene, diisopropypenylbenzene and combinations thereof. In a particularly preferred embodiment, the vinylaromatic monomer is selected from divinylbenzene, styrene and combinations thereof.

[0056] The mini -emulsion process also includes the addition of a co-stabilizer in the dispersed (organic phase). The use of the co-stabilizer is another contrast to suspension polymerization processes, such as those used to make carbon microparticles. The co-stabilizer is added to prevent Ostwald ripening or coalescence of smaller particles that merge together to create larger particles. The co-stabilizer may be selected from Cio - C22 alkyl, C10 - C22 aliphatic alcohol, non-“ surface-active” polymers, and combinations thereof. In some embodiments, the co-stabilizer is selected from Cio - Ci8 alkyl, Cio - Ci8 aliphatic alcohol and combinations thereof. In a particularly preferred embodiment, the co-stabilizer is selected from the group consisting of hexadecane, cetyl alcohol and combinations thereof.

[0057] In methods used to produce porous nanospheres, a porogen is also included in the dispersed phase to control the pore size distribution of the resulting polymeric nanospheres. Porogens, formerly referred to as phase extenders, are solvents that are added to polymerization to affect the properties of the polymer being formed. Porogens can affect many properties of a polymer, including, but not limited to surface area, pore volume, pore size, porosity, and hydrophobic-hydrophilic properties. Particular porogens, or combinations of porogens are preferably added to tune the properties of the resulting polymer. Suitable porogens may be selected from solvating porogens, i.e., porogens miscible in the polymer and monomer, non-solvating porogens, i.e., those with poor miscibility with the polymer, in particular, and combinations thereof.

[0058] Some exemplary porogens include toluene, xylenes, benzene, hexane, cyclohexane, pentane, heptane, octane, nonane, decane, dodecane, isooctane, dichloromethane, chloroform, carbon tetrachloride, benzyl alcohol, butanol, pentanol, hexanol, heptanol, 4-methyl -2-pentanol, isoamyl alcohol, dodecanol, ethyl acetate, 2-ethylhexanol, cyclohexanol, and combinations thereof. One skilled in the art would also be able to choose additional porogens to tune the properties of the resulting polymers. In a particularly preferred embodiment, a combination of o-xylene and 4-methyl-2-pentanol are used for porogens.

[0059] During typical mini-emulsion processes, the mini-emulsion is usually agitated through means such as ultracentrifugation or homogenization. Using the methods described herein, the inventors were able to obtain nanometer-sized particles using lower agitation with an overhead stirrer at 500 rpm. Accordingly, a homogenizer or stir paddle system may be used during the mini-emulsion process described herein.

[0060] The porous spherical nanopolymer is then polysulfonated. Polysulfonation of the polymer nanospheres may be achieved by contacting the polymer nanospheres resulting from the processes described above with an amount of fuming sulfuric acid for a period ranging from about five hours to about 72 hours at a temperature ranging from about 150°C up to the polymer degradation temperature of the polymer nanospheres. The amount of fuming sulfuric acid may range from about 100% and about 2000% of the total weight of the polymer nanosphere particles.

[0061] Fuming sulfuric acid, as defined herein, refers to a solution of sulfur trioxide in sulfuric acid. When contacted with the polymer nanospheres, both sulfonate and sulfone groups may covalently bind to available carbons in the polymer nanospheres. In addition, sulfone crosslinks may form from non- crosslinked carbons in the polymer nanospheres.

[0062] Unlike conventional polysulfonization processes, which are preferably carried out at 120°C, the methods described herein employ a higher temperature for this step. In a preferred embodiment, the polysulfonization process described herein is carried out at 150°C. The polysulfonization step may also be carried out at temperatures above 150°C, provided the temperature is below the polymer degradation temperature. The higher temperature helps to stabilize the sulfur complex on the polymer ring structures when neutralizing with water. Polysulfonating at 150°C improves the stability of the sulfur-carbon bonds during neutralization. Furthermore, at 150°C, the theoretical bonding level of 1.6 sulfur groups per benzene ring structure is ensured, and the resultant carbon pore structure was found to be effective and repeatable.

[0063] In one embodiment, polysulfonization is carried out by (a) cautiously adding sulfuric acid to the porous spherical nanopolymer at a ratio in which the amount of S is in excess of the number of ring structures in the polymer; (b) heating the combination from the above step to a temperature of just below the melting point of the porous spherical nanopolymer and (c) maintaining the reaction at the temperature of just below the melting point of the porous spherical nanopolymer for a time sufficient to complete the polysulfonization. The sulfuric acid is added at a ratio of at least 1.6 S: 1 ring structure of the porous spherical nanopolymer. Preferably, a ratio of greater than 1.6 S: 1 ring structure, i.e., 2 S: 1 ring structure, or even greater is used. The reaction temperature is maintained to at least 150°C, or potentially higher if the polymer degradation temperature allows.

[0064] In another embodiment, polysulfonization is carried out by cautiously adding sulfuric acid to the porous spherical nanopolymer, wherein the sulfuric acid is added at a ratio of 1 : 10 sulfuric acid:porous spherical polymer (wt.:wt.); heating the combination from the above step to about 150°C; and maintaining the reaction at 150°C for a time sufficient to complete the polysulfonization.

[0065] After the completion of polysulfonation, the polymer nanospheres may be neutralized by rinsing the particles in deionized water, while maintaining the temperature of the mixture of water and particles below about 100°C.

[0066] Following polysulfonization, the polysulfonated porous polymer

nanospheres are subjected to pyrolysis to produce the inventive carbon nanospheres. Pyrolysis is carried out by heating the the polysulfonated porous polymer nanospheres at temperature in the range from about 300°C to about 1200°C for a time sufficient for pyrolysis of the polymer to complete to yield the carbon nanospheres. Typically, pyrolysis is performed for a period ranging from about 15 minutes to about two hours.

[0067] A fluidized bed treatment may be used for the pyrolysis; in that

embodiment, heated nitrogen is passed upward through a bed of polysulfonated polymer nanospheres. In this embodiment, the gas serves to agitate as well as to heat the particles.

[0068] In another embodiment, a static bed may be used for pyrolysis. For example, the polysulfonated polymer nanospheres may be loaded into quartz trays and loaded into a thermal furnace and heated to a temperature of about 1100° C for about two hours under inert gas sweep. The resulting carbonaceous nanospheres may be removed from the thermal furnace after cooling the oven to room temperature. [0069] Optionally, the resulting carbon nanospheres may be activated through an activation step. The activation step involves contacting the porous spherical nanocarbons with a physical activation gas a temperature in the range from about 300°C to about 1200°C. The physical activation gas may be selected from steam, oxygen, carbon dioxide or a combination thereof.

[0070] Steam activation may widen the micropores within the porous spherical nanocarbons by a process in which the water vapor dissociates and reacts with the porous spherical nanocarbons. The oxygen component of the dissociated steam may react with carbon in the framework of the carbonaceous particles to form CO2 and/or CO, which outgases from the particles. The steam activation process may create new pores by the removal of carbon from the porous spherical nanocarbons and may also reopen pores closed by the initial pyrolysis process described above. Any adsorbed compounds trapped within the pores of the porous spherical nanocarbons may be solubilized and removed from the particles during the activation processes.

[0071] In one embodiment, the steam activation process is performed by placing porous spherical nanocarbons in a Lindberg vertical furnace and attaching a source of steam to the inlet line of the furnace. The steam activation process may be performed for a period of time sufficient to ensure that the maximum number of pores has opened up in the carbon nanospheres, and to ensure that the desired pore diameter is achieved.

[0072] The size of the pores within the carbon nanospheres may be manipulated to predetermined values by specifying the duration and temperature at which the steam activation is performed. Longer durations and higher activation temperatures may be associated with larger and more numerous pores in the carbon nanospheres.

[0073] In another embodiment, the steam activation of the carbon nanospheres may be conducted at a temperature ranging from about 600°C and about 1,000°C. In some embodiments, steam activation is carried out in the range from about 700°C to about 900°C. In an additional embodiment, the steam activation of the carbon nanospheres may be conducted at a temperature of about 850°C.

[0074] In another additional embodiment, other activation processes including but not limited to liquid-phase activation, chemical activation, compressed air activation, or any combination thereof may be employed to activate the carbon nanospheres.

[0075] The activated carbon nanospheres may be subjected to a second pyrolysis treatment to reduce the overall size of the pores within the particles and which may also provide a more hydrophobic carbon surface. The desired overall size of the pores within the particles may be selected to impart specificity for the adsorption of particular compounds based on the internal diameter of ultramicropores. The resulting internal diameters of the pores within the carbon nanospheres after post-activation pyrolysis may depend upon the temperature and duration at which the pyrolysis is conducted.

[0076] In one embodiment, the post-activation pyrolysis is conducted at a temperature ranging from about 560°C and about 1300°C. In another embodiment, the post-activation pyrolysis is conducted at a temperature in the range from about 800°C and about 1200°C. In another embodiment, the post activation pyrolysis is conducted at a temperature of about 1150°C.

[0077] In some embodiments, the carbon nanospheres are graphitized.

Graphitization, or carbonization, may be carried out on the pyrolyzed or pyrolyzed/activated carbon nanospheres by heating to a temperature of at least 2500°C, results in a graphitized, spherical polymer carbon. This carbon possesses an external layering of graphitic carbon with an amorphous internal carbon structure. This layer is typically about 2% of the total carbon mass. The graphitic/amorphous hybrid carbon is stable at high pressure of approximately 10,000 psi and does not fracture during vibration. Figure 10 is a low-resolution SEM image of a graphitized, spherical polymer carbon. [0078] In some embodiments, the graphitic carbon on the carbon nanospheres is about 1% to about 40% of the carbon by weight. In a preferred embodiment, the graphitic carbon is about 1% to about 3% of the carbon by weight.

[0079] In some embodiments, the carbon nanospheres may further include an adsorptive coating, such as a coating suitable for GC, SPE, or other adsorptive process.

[0080] Further provided are devices including the spherical nanocarbons

disclosed herein. In some embodiments, such devices may include, for example, filtration devices, electrical devices, chromatography columns, solid phase extraction cartridges, solid phase microextraction fibers, thermal desorption tubes, bulk preparation devices, batteries, electrodes and drug delivery devices. In such devices, the spherical nanocarbons described herein may be used in place of, or in addition to, conventional carbons, such as carbon microspheres such as the Carboxen® carbons available from Supelco Inc., or other conventional particles.

[0081] Also disclosed with the above-described subject matter:

[0082] (1) Carbon nanospheres comprising at least 99% carbon by weight and having a diameter in the range from about 10 nm to 900 nm.

[0083] (2) The carbon nanospheres of item (1) wherein the carbon nanospheres have a diameter in the range from about 200 nm to about 800 nm.

[0084] (3) The carbon nanospheres of item (1) or item (2) wherein the

nanospheres are monodisperse.

[0085] (4) The carbon nanospheres of item (1) wherein the spherical nanocarbon has a surface area in the range from about 1 m²/g to about 4000 m²/g.

[0086] (5) The carbon nanospheres of item (1) wherein the carbon nanospheres comprise a plurality of pores. [0087] (6) The carbon nanospheres of item (5) wherein the pores are selected from micropores, mesopores, macropores, ultramicropores, and combinations thereof.

[0088] (7) The carbon nanospheres of item (6) wherein the carbon nanospheres comprise primarily micropores.

[0089] (8) The carbon nanospheres of item (6) wherein the carbon nanospheres comprise primarily mesopores.

[0090] (9) The carbon nanospheres of item (3) wherein the carbon nanospheres comprise primarily macropores.

[0091] (10) The carbon nanospheres of item (6) wherein the carbon

nanospheres comprise a combination of micropores, mesopores and macropores.

[0092] (11) The carbon nanospheres of item (6) wherein the carbon nanospheres comprise a combination of micropores and macropores.

[0093] (12) The carbon nanospheres of item (11) wherein the ratio of micropores to macropores in the range from about 1% to about 99%.

[0094] (13) The carbon nanospheres of item (5) wherein the carbon nanospheres are fully porous.

[0095] (14) The carbon nanospheres of item (5) wherein the carbon nanospheres have an open pore structure.

[0096] (15) The carbon nanospheres of item (5) wherein the carbon nanospheres have a closed pore structure.

[0097] (16) The carbon nanospheres of item (2) comprising a combination of open pores and closed pores.

[0098] (17) The carbon nanospheres of item (1) wherein the carbon nanosphere is nonporous. [0099] (18) The carbon nanospheres of item (1) further comprising an external layer of graphitic carbon on the spherical nanocarbon.

[0100] (19) The carbon nanospheres of item (18) wherein the graphitic carbon comprises about 1% to about 40% of the carbon by weight.

[0101] (20) The carbon nanospheres of item (19) wherein the graphitic carbon comprises about 1% to about 3% of the carbon by weight.

[0102] (21) The carbon nanospheres of item (1) further comprising an adsorptive coating.

[0103] (22) The carbon nanospheres of item (21) wherein the adsorptive coating is a polymeric coating.

[0104] (23) A method for preparing a porous spherical nanocarbon, the method comprising the steps of forming a porous spherical nanopolymer through a miniemulsion process; polysulfonating the porous spherical nanopolymer to form a

polysulfonated porous spherical nanopolymer; drying the polysulfonated porous spherical nanopolymer; pyrolyzing the polysulfonated porous spherical nanopolymer to yield a porous spherical nanocarbon, and optionally, activating the porous spherical nanocarbon.

[0105] (24) The method of item (23) further comprising the step of graphitizing the porous spherical nanocarbon by thermally treating the porous spherical nanocarbon at a temperature of at least 2500°C.

[0106] (25) The method of item (23) wherein the miniemulsion process comprises the steps of providing a dual phase mixture having an aqueous phase and an organic phase, wherein the aqueous phase comprises an aqueous solvent, a water-soluble initiator and a surfactant wherein the concentration of surfactant is below the critical micelle concentration for the surfactant; and wherein the organic phase comprises a vinylaromatic monomer, a co stabilizer and a porogen; applying sufficient shear to the dual phase mixture to form an emulsion; and heating the emulsion to 70°C with shear mixing until the polymerization reaction is complete, yielding the porous spherical nanopolymer.

[0107] (26) The method of item (25) wherein the initiator is selected from the group consisting of thermal initiators and redox initiators.

[0108] (27) The method of item (26) wherein the initiator comprises a thermal initiator selected from the group consisting of ammonium persulfate, potassium persulfate, lauroyl peroxide, benzoyl peroxide, 2,2-azobisisobutyronitrile and combinations thereof.

[0109] (28) The method of item (26) wherein the initiator comprises a redox initiator selected from the group consisting of ammonium persulfate/sodium sulfite, ammonium persulfate/tetramethyl ethylene diamine, hydrogen peroxide/sodium formaldehyde sulfoxylate and combinations thereof.

[0110] (29) The method of item (25) wherein the surfactant comprises an anionic surfactant.

[0111] (30) The method of item (29) wherein the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, potassium oleate and combinations thereof [0112] (31) The method of item (25) wherein the surfactant comprises a cationic surfactant.

[0113] (32) The method of item (31) wherein the surfactant is selected from the group consisting of cetyltrimethylammonium bromide,

cetyltrimethylammonium chloride, octadecyl pyridium bromide and

combinations thereof.

[0114] (33) The method of item (25) wherein the surfactant is a nonionic

surfactant.

[0115] (34) The method of item (33) wherein the surfactant is selected from the group consisting of polyethylene oxide derivatives, and nonylphenol polyethoxylate with an average of 40 ethylene oxide units.

[0116] (35) The method of item (25) wherein the vinylaromatic monomer is selected from the group consisting of divinylbenzene, styrene, alpha

methylstyrene, vinyltoluene, p-methyl styrene, ethyl-vinylbenzene,

vinylnaphthalene, trivinylbenzene, vinylisopropenylbenzene,

diisopropypenylbenzene and combinations thereof.

[0117] (36) The method of item (35) wherein the vinylaromatic monomer is selected from the group consisting of divinylbenzene, styrene and combinations thereof.

[0118] (37) The method of item (25) wherein the co-stabilizer is selected from the group consisting of Cio - C22 alkyl, C10 - C22 aliphatic alcohol and combinations thereof.

[0119] (38) The method of item (37) wherein the co-stabilizer is selected from the group consisting of Cio - Ci8 alkyl, Cio - Ci8 aliphatic alcohol and combinations thereof. [0120] (39) The method of item (38) wherein the co-stabilizer is selected from the group consisting of hexadecane, cetyl alcohol and combinations thereof.

[0121] (40) The method of item (25) wherein the porogen is selected from the group consisting of solvating porogens, non-solvating porogens and

combinations thereof.

[0122] (41) The method of item (40) wherein the porogen comprises o-xylene and 4-methyl -2-pentanol.

[0123] (42) The method of item (23) wherein the step of polysulfonating the porous spherical nanopolymer comprises the steps of

(a) cautiously adding sulfuric acid to the porous spherical nanopolymer at a ratio in which the amount of S is in excess of the number of ring structures in the polymer;

(b) heating the combination from the above step to a temperature of just below the polymer degradation point of the porous spherical nanopolymer and

(c) maintaining the reaction at the temperature of just below the melting point of the porous spherical nanopolymer for a time sufficient to complete the polysulfonization.

[0124] (43) The method of item (23) wherein the sulfuric acid is added to the porous spherical nanopolymer at a ratio of at least 1.6 S: 1 ring structure of the porous spherical nanopolymer.

[0125] (44) The method of item (23) wherein the step of polysulfonating the porous spherical nanopolymer comprises the steps of cautiously adding sulfuric acid to the porous spherical nanopolymer, wherein the sulfuric acid is added at a ratio of 1 : 10 sulfuric acid:porous spherical polymer (wt.:wt.); heating the combination from the above step to about 150°C; and maintaining the reaction at 150°C for a time sufficient to complete the polysulfonization.

[0126] (45) The method of item (23) wherein the pyrolyzing step comprises heating the polysulfonated porous spherical nanopolymer at temperature in the range from about 300°C to about 1200°C for a time sufficient for pyrolysis of the polymer to complete.

[0127] (46) The method of item (23) wherein the optional activation step

comprises contacting the porous spherical nanocarbon with a physical activation gas a temperature in the range from about 300°C to about 1200°C.

[0128] (47) The method of item (46) wherein the physical activation gas is selected from the group consisting of steam, oxygen, carbon dioxide or a combination thereof.

[0129] (48) A method for preparing a spherical nanocarbon, the method

comprising the steps of

(a) forming a spherical nanopolymer through a miniemulsion process; the miniemulsion process comprising the steps of

(i) providing a dual phase mixture having an aqueous phase and an organic phase, wherein the aqueous phase comprises an aqueous solvent, a water-soluble initiator and a surfactant wherein the concentration of surfactant is below the critical micelle concentration for the surfactant; and wherein the organic phase comprises a vinylaromatic monomer and a co stabilizer;

(ii) applying sufficient shear to the dual phase mixture to form an emulsion; and (iii) heating the emulsion to 70°C with shear mixing until the polymerization reaction is complete, yielding the spherical nanopolymer;

(b) polysulfonating the spherical nanopolymer to form a polysulfonated spherical nanopolymer, the polysulfonating comprising the steps of

(i) cautiously adding sulfuric acid to the spherical nanopolymer at a ratio in which the amount of S is in excess of the number of ring structures in the polymer;

(ii) heating the combination from step (b)(i) to a temperature of about 150°C and

(iii) maintaining the reaction at the temperature of about 150°C for a time sufficient to complete the polysulfonization;

(c) drying the polysulfonated spherical nanopolymer;

(d) pyrolyzing the polysulfonated spherical nanopolymer at temperature in the range from about 300°C to about 1200°C for a time sufficient for pyrolysis of the polymer to complete to yield a spherical nanocarbon, and optionally, activating the spherical nanocarbon.

[0130] (49) The method of item (48) further comprising the step of graphitizing the spherical nanocarbon by thermally treating the spherical nanocarbon at a temperature of at least 2500°C.

[0131] (50) A device comprising the spherical nanocarbon of item (1).

[0132] (51) The device of item (50) wherein the device is a filtration device.

[0133] (52) The device of item (50) wherein the device is an electrical device.

[0134] (53) The devices of item (50) wherein the device is selected from

chromatography columns, solid phase extraction cartridges, solid phase microextraction fibers, thermal desorption tubes, bulk preparation devices, batteries, electrodes and drug delivery devices.

[0135] Example

[0136] Synthesis of polymer nanospheres

[0137] A standard reaction set-up using a 3000 mL flask, homogenizer,

condenser, N2 purge, and temperature probe w/ programmable controller. The aqueous phase was added to the flask, followed by the organic phase.

Homogenization was started after addition of the aqueous phase. Once the organic phase was added, the homogenization rate was increased. The solution turned from a 2-layer clear liquid to a white continuous phase. Heating was started immediately to 70°C. The reaction was carried out for about 3 hours.

[0138] Synthesis filtering of polymer nanospheres

[0139] After synthesis, the polymer was filtered and washed using a filtering centrifuge. The contents of the flask were poured into a funnel which would feed into the basket. Using a polypropylene bag, particles were separated from the liquid. A line was connected for the outlet feed which emptied into a waste bucket. The contents were washed with copious amounts of methanol. After removal of the methanol, the contents were left to spin for about 15 minutes before shutting down the centrifuge.

[0140] Polysulfonation of polymer nanospheres

[0141] A polysulfonation reaction setup was assembled which included a 4-neck 5000mL round bottom flask, reflux condenser, addition funnel and temperature probe. The previously synthesized polymer was added to the flask. Stirring commenced while 2000 mL H2SO4 was cautiously added dropwise through the addition funnel. Addition of H2SO4 was temporarily stopped when the temperature reached 70°C. Stirring was stopped and done manually until the contents became fluid. Once the reactor had cooled to about 45°C, addition of acid was resumed. This process was repeated until the temperature started to drop even with acid addition. The remaining acid was then added through the addition funnel. Heat was applied and set to 150°C. Once 150°C was reached, heating continued for 4 hours.

[0142] Neutralization

[0143] Neutralization was accomplished by SLOWLY adding water at ambient temperature, and not allowing the reaction pot to exceed a temperature of 80°C.

[0144] Filtration Post-neutralization

[0145] To the reactor, 3 L of DI ¾0 was added. The reactor assembly was dismantled and the contents were emptied into a 10L bucket. An additional 1500mL of DI ¾0 was added and was stirred manually. A filtration apparatus was set up using 0.1 pm filter paper. Once all of the contents had been initially filtered of the acidic solution, washing was conducted with copious amounts of DI water. A final wash with 1 L MeOH was done. The material was left to dry in the filter, then transferred to a glass baking dish and was covered. The dish was placed in a vacuum oven. Ambient conditions were held for a few hours, followed by heating to 80°C for a time sufficient to complete the drying.

[0146] Carbonization/Pyrolysis

[0147] Pyrolysis was performed using a quartz combustion tube positioned in a horizontal tube furnace. The thermal profile followed is summarize in the table below:

[0148] Nitrogen gas was passed through the combustion tube at a flow rate of 50 - 500 mL/minute. The effluent was trapped in an impinger, and subsequently vented to an appropriate scrubber and hood.

[0149] Activation (steam and carbon dioxide)

[0150] Activation was performed using a quartz combustion tube, positioned in a horizontal tube furnace. The thermal profile followed in summarized in the table below:

[0151] Steam activation was accomplished by bubbling nitrogen gas through a round-bottom flask containing heated water. A flow rate of 100 mL/minute was used. [0152] Carbon dioxide activation was accomplished by passing 100% CO2 at 100 mL/minute, using the same thermal profile.

[0153] Oxygen (compressed air) activation was accomplished by passing 100% air at 100 mL/minute, using a similar profile.

[0154] The Examples herein are for illustration and are not meant to limit the scope of the invention as defined by the claims.

Claims

The invention claimed is:

1. Carbon nanospheres comprising at least 99% carbon by weight and having a diameter in the range from about 10 nm to 900 nm, preferably in the range from about 200 nm to about 800 nm.

2. The carbon nanospheres of claim 1 wherein the nanospheres are

monodisperse.

3. The carbon nanospheres of claim 1 or claim 2 wherein the spherical

nanocarbon has a surface area in the range from about 1 m²/g to about 4000 m²/g.

4. The carbon nanospheres of claims 1, 2 or 3 wherein the carbon

nanospheres comprise a plurality of pores.

5. The carbon nanospheres of claim 4 wherein the pores are selected from micropores, mesopores, macropores, ultramicropores, and combinations thereof.

6. The carbon nanospheres of claim 5 wherein the carbon nanospheres

comprise a combination of micropores and macropores.

7. The carbon nanospheres of claim 1 wherein the carbon nanosphere is nonporous.

8. The carbon nanospheres of any of claims 1-7 further comprising an

external layer of graphitic carbon on the spherical nanocarbon, wherein the graphitic carbon comprises about 1% to about 40% of the carbon by weight, preferably about 1% to about 3% of the carbon by weight.

9. The carbon nanospheres of any of claims 1-8 further comprising an

adsorptive coating.

10. The carbon nanospheres of claim 9 wherein the adsorptive coating is a polymeric coating.

11. A method for preparing a porous spherical nanocarbon, the method

comprising the steps of forming a porous spherical nanopolymer through a miniemulsion process; polysulfonating the porous spherical nanopolymer to form a

polysulfonated porous spherical nanopolymer; drying the polysulfonated porous spherical nanopolymer; pyrolyzing the polysulfonated porous spherical nanopolymer to yield a porous spherical nanocarbon, and optionally, activating the porous spherical nanocarbon.

12. The method of claim 11 wherein the miniemulsion process comprises the steps of providing a dual phase mixture having an aqueous phase and an organic phase, wherein the aqueous phase comprises an aqueous solvent, a water-soluble initiator, preferably a thermal initiator or a redox initiator, and a surfactant wherein the concentration of surfactant is below the critical micelle concentration for the surfactant; and wherein the organic phase comprises a vinylaromatic monomer, a co-stabilizer and a porogen; applying sufficient shear to the dual phase mixture to form an emulsion; and heating the emulsion to 70°C with shear mixing until the polymerization reaction is complete, yielding the porous spherical nanopolymer.

13. The method of claim 11 or 12 further comprising the step of graphitizing the porous spherical nanocarbon by thermally treating the porous spherical nanocarbon at a temperature of at least 2500°C.

14. The method of claim 12 wherein the surfactant comprises an anionic

surfactant, wherein the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, potassium oleate and combinations thereof

15. The method of claim 12 wherein the surfactant comprises a cationic

surfactant, wherein the surfactant is selected from the group consisting of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, octadecyl pyridium bromide and combinations thereof.

16. The method of claim 12 wherein the surfactant is a nonionic surfactant, wherein the nonionic surfactant is selected from the group consisting of polyethylene oxide derivatives, and nonylphenol polyethoxylate with an average of 40 ethylene oxide units.

17. The method of claim 12 wherein the vinylaromatic monomer is selected from the group consisting of divinylbenzene, styrene, alpha-methylstyrene, vinyltoluene, p-methyl styrene, ethyl-vinylbenzene, vinylnaphthalene, trivinylbenzene, vinylisopropenylbenzene, diisopropypenylbenzene and combinations thereof, and is preferably selected from the group consisting of divinylbenzene, styrene and combinations thereof.

18. The method of claim 12 wherein the co-stabilizer is selected from the

group consisting of Cio - C22 alkyl, C10 - C22 aliphatic alcohol and combinations thereof, prefereably selected from the group consisting of Cio - Ci8 alkyl, Cio - Ci8 aliphatic alcohol and combinations thereof, and more preferably selected from the group consisting of hexadecane, cetyl alcohol and combinations thereof.

19. The method of claim 12 wherein the porogen is selected from the group consisting of solvating porogens, non-solvating porogens and

combinations thereof, preferably the porogen comprises o-xylene and 4- methyl-2-pentanol.

20. The method of claim 11 wherein the step of polysulfonating the porous spherical nanopolymer comprises the steps of

(a) cautiously adding sulfuric acid to the porous spherical nanopolymer at a ratio in which the amount of S is in excess of the number of ring structures in the polymer, preferably the sulfuric acid is added to the porous spherical nanopolymer at a ratio of at least 1.6 S: 1 ring structure of the porous spherical nanopolymer;

(b) heating the combination from the above step to a temperature of just below the polymer degradation point of the porous spherical nanopolymer, preferably to about 150°C and

(c) maintaining the reaction at the temperature of just below the melting point of the porous spherical nanopolymer, preferably about 150°C for a time sufficient to complete the polysulfonization.

21. A method for preparing a spherical nanocarbon, the method comprising the steps of

(a) forming a spherical nanopolymer through a miniemulsion process; the miniemulsion process comprising the steps of

(i) providing a dual phase mixture having an aqueous phase and an organic phase, wherein the aqueous phase comprises an aqueous solvent, a water-soluble initiator and a surfactant wherein the concentration of surfactant is below the critical micelle concentration for the surfactant; and wherein the organic phase comprises a vinylaromatic monomer and a co-stabilizer;

(ii) applying sufficient shear to the dual phase mixture to form an emulsion; and

(iii) heating the emulsion to 70°C with shear mixing until the polymerization reaction is complete, yielding the spherical nanopolymer;

(b) polysulfonating the spherical nanopolymer to form a polysulfonated spherical nanopolymer, the polysulfonating comprising the steps of

(i) cautiously adding sulfuric acid to the spherical nanopolymer at a ratio in which the amount of S is in excess of the number of ring structures in the polymer;

(ii) heating the combination from step (b)(i) to a temperature of about 150°C and

(iii) maintaining the reaction at the temperature of about 150°C for a time sufficient to complete the polysulfonization;

(c) drying the polysulfonated spherical nanopolymer;

(d) pyrolyzing the polysulfonated spherical nanopolymer at temperature in the range from about 300°C to about 1200°C for a time sufficient for pyrolysis of the polymer to complete to yield a spherical nanocarbon, and

optionally, activating the spherical nanocarbon.

22. The method of claim 21 further comprising the step of graphitizing the spherical nanocarbon by thermally treating the spherical nanocarbon at a temperature of at least 2500°C.

23. A device comprising the spherical nanocarbon of claim 1.

24. The device of claim 23 wherein the device is a filtration device.

25. The device of claim 23 wherein the device is an electrical device.

26. The devices of claim 23 wherein the device is selected from

chromatography columns, solid phase extraction cartridges, solid phase microextraction fibers, thermal desorption tubes, bulk preparation devices, batteries, electrodes and drug delivery devices.