WO2018071805A1

WO2018071805A1 - Surface modified carbonized materials

Info

Publication number: WO2018071805A1
Application number: PCT/US2017/056569
Authority: WO
Inventors: Serguei USMANOV
Original assignee: Immutrix Therapeutics Inc
Current assignee: Immutrix Therapeutics Inc
Priority date: 2016-10-14
Filing date: 2017-10-13
Publication date: 2018-04-19
Anticipated expiration: 2019-04-14

Abstract

An activated carbon particle having a surface comprising a hydrophobic portion and a hydrophilic portion wherein the hydrophilic portion contains at least one carbon nanoparticle extending away from the surface of the activated carbon particle. A method of preparing a carbon composition comprising contacting an activated carbon bead composition with graphene nanoparticles using graphene-containing electrically conductive electrode, a DC voltage power supply with an applied voltage of greater than about 1.28 VDC, an aprotic electrolyte with DC electrical resistance less than about 18 Ohm/cm. A composition comprising active carbon particle having an electrically charged moiety attached to the surface of the active carbon particles wherein the active carbon particles without an attached electrically charged moiety.

Description

SURFACE MODIFIED CARBONIZED MATERIALS

CROSS-REFERENCE TO INCORPORATED APPLICATIONS

[001] This application claims priority to, and incorporates by reference in its entirety, U.S. Provisional Patent Application Serial No. 62/408,487, filed October 14, 2016 and entitled "Surface Modified Carbonized Materials."

TECHNICAL FIELD

[002] The present disclosure relates to novel carbonaceous materials and methods of making and using same. The present disclosure also relates to methods of increasing the hydrophilicity of a carbonaceous material.

BACKGROUND

[003] Carbon and its allotropes, graphite, diamond, and amorphous carbon, have been widely utilized in applications ranging from shoe polish to batteries. The absence of functional groups renders carbon materials hydrophobic, however, functionalization of carbon materials to alter the surface chemistry has traditionally posed a challenge in chemistry and engineering.

[004] For example, traditional methods for surface oxidation of carbon materials are characterized as both time consuming and often require extensive heating. Additionally, such oxidation methods typically require filtration and washing of the functionalized carbon materials in order to remove the oxidant. Such additional processing detrimentally impacts the manufacturing costs for these materials and products utilizing same by, for example, increasing the cost for commercialization of products incorporating the functionalized carbon materials. Thus, an ongoing need exists for novel methods of functionaiizing hydrophobic carbonaceous material and methods of using such materials,

SUMMARY

[005] Disclosed herein is an activated carbon particle having a surface comprising a hydrophobic portion and a hydrophilic portion wherein the hydrophilic portion contains at least one carbon nanoparticle extending away from the surface of the activated carbon particle.

[006] Also disclosed herein is a method of preparing a carbon composition comprising contacting an activated carbon bead composition with graphene nanoparticles using graphene-containing electrically conductive electrode, a DC voltage power supply with an applied voltage of greater than about 1.28 VDC, an aprotic electrolyte with DC electrical resistance less than about 18 Ohm/cm .

[007] Also disclosed herein is a composition comprising active carbon particle having an electrically charged moiety attached to the surface of the active carbon particles wherein the active carbon particles have a porosity within 5% of a porosity of otherwise similar active carbon particles without an attached electrically charged moiety.

[008] Also disclosed herein is method comprising electrochemical deposition of carbon nanostructure on to a surface of an activated carbon particle to generate a hydrophilic activated carbon particle.

[009] Also disclosed herein is a composition comprising an activated carbon particle having a surface comprising a hydrophobic portion and a hydrophilic portion wherein the hydrophilic portion contains at least one carbon nanopaiticle extending away from the surface of the activated carbon particle and wherein the nanopaiticle has an electrical charge.

[010] Also disclosed herein is a radar absorbing material comprising active carbon particles having an electrically charged moiety attached to the surface of the active carbon particles wherein the electrically charged moiety

[011] Also disclosed herein is method of preparing a carbon composition comprising (a) functionalizing a carbon nanostructure to generate a functionalized carbon nanostructure; and (b) electrochemically attaching the functionalized carbon nanostructure to an activated carbon bead to generate a functionalized activated carbon bead having an electrical charge.

DESCRIPTION OF THE DRAWING

[012] Figure 1 is an example of a structure of a composition of the present disclosure.

DETAILED DESCRIPTION

[013] Disclosed herein are functionalized carbon materials that exhibit increased hydrophilicity. The functionalized carbon material comprises a first carbon component and a second carbon component. In an aspect, the first carbon component comprises a hydrophobic carbonaceous material. In an aspect, the second carbon component comprises a carbon nanopaiticle. A functionalized carbon material of the present disclosure has the second carbon component permanently attached to the first carbon component. In an aspect, the permanently attached second carbon component is associated with the first carbon component via a carbon-carbon covalent bond. [014] In an aspect, a functionalized carbon material of the present disclosure is characterized by a permanent surface charge, a tunable charge intensity, and a dipole magnetic moment which can be directly correlated to the diameter and length of the second carbon component (i.e., carbon nanoparticie). In an aspect, a functionalized carbon material comprises a carbonaceous material (e.g., a carbon bead (CB)) as the first carbon component and a carbon nanostructure (CNS) as the second carbon component and is designated CNS-CB.

[015] In an aspect, a CNS-CB of the present disclosure is characterized as (i)hydrophilic; (ii) has the ability to facilitate water adsorption und er ambient conditions that reduces the buoyancy of the CNS-CB in an aqueous fluid; (iii) partially dissociation of the CNS from the CB with a concomitant increase in hydrophobicity sufficient to allow collection of the CNS-CB by simple gravimetrical separation; (iv) a reduced formation of th e CNS-CB clusters, (v) elimination of cake formation and plugging of filtration screens and filtration housings; (vi) elimination of channeling phenomena during liquid flow through the bulk of CNS-CB; (vii) hydrophiiic properties which are retained after drying of the CNS-CB; (viii) the creation of stable water-insoluble carbon nanostructures on the hydrophobic surface and inside the pores of the carbonaceous material (e.g., carbon bead); (ix) the CNS-CB may prevent direct interaction of blood cells with the hydrophobic surface of the carbonaceous material (e.g., a carbon bead) thus minimizing of one or more platelet activation cascades; and (x) able to react with additional functionalities and chemical groups so as to provide a plurality of reactive surface moieties.

[016] In an aspect, a carbonaceous material for use in the present disclosure as a first carbon component may be characterized as having a reduced wettability. For example, a carbonaceous material suitable for use as a first carbon component in a functionalized carbon material, (i.e., a CB ) when contacted with liquid water under nominal conditions may display at least three different behavior patterns for the bulk CB. One behavior pattern involves the CB sinking in the liquid to the bottom of the container immediately after introduction. Subsequently, the submerged CB forms clusters which eventually become sufficiently buoyant to float to the surface of the water. In particular, the submerged CB can be observed to emit bubbles of gas (air) which transport particles of the CB. Subsequent to reemergence at the surface of the liquid, contact with air at liquid surface causes rupture of the air bubbles and release of the CB particles which again are submerged and settle to the bottom of the container. In an aspect the process of emergence from and submergence in the liquid is a steady state process which can progress for hours (2-3 hours slightly depending of ambient temperature). In an aspect, another behavior involves a substantial portion of the CB, from about 7 weight percent (wt.%) to about 10 wt.% of the bulk of the CB remains the on surface of the water and will not submerge. In such aspects, external vigorous mixing of the liquid facilitates additional CB submergence. In an aspect, at least a portion of the ACB involved in the steady state process of submergence and reemergence form clusters ranging in diameter of from about 4 mm to about 5 mm which precipitate as intact entities.

[017] A third class of CB materials is characterized by the behavior of adhering to the surface of the container and is therefore unavailable to participate in the steady state process of submergence and reemergence. Consequently, the following three classes are defined as: Class #1 particles which rapidly submerge and display strong adhesion to the bottom of the vessel. Class#2 particles which participate in the steady state process of submergence and reemergence with stable cluster formation. Class#3 particles which remain sufficiently buoyant to float on the surface of the liquid without submergence even with agitation.

[018] The present disclosure relates to a process for the creation of uniform charges on a carbonaceous material, for example a carbon particle such as a bead, alternatively an activated carbon particle. The creation of a charged surface on such materials presents an opportunity for coating the exposed surfaces of the carbon material (e.g., CB) with compounds that attenuate the adsorption selectivity characteristics of the carbon material. Without wishing to be limited by theory, establishment of a uniform charge distribution not only on external surfaces of the first carbon component (e.g., CB) but also on the inside of the pore walls provides an opportunity to drastically improve distribution of coating agents through and around the porous structure of the first carbon component thereby engaging the entire morphology of the material in the separation and adsorption processes.

[019] In an aspect, the functionalized carbon material of the present disclosure avoids the drawbacks associated with other methods of carbon functionalization by the introduction of carbon nanostructures on surfaces of a carbon material without the introduction of other ions or contaminants that may compromise the chemical purity of the carbon material. In an aspect, the nanomorphology of the second carbon component creates a differentiation of electric and electro dipole properties of the functionalized carbon material thereby modifying the local electric field. Without wishing to be limited by theory, the resultant modification of the local electric field provides for minimal interaction with the electron density distribution along the macroparticies as propagation of electro-dipole momentum through the second carbon component is defined by different structural laws of quantum mechanical symmetry.

[020] In an aspect, the functionalized carbon material is oxidized via oxidation of the second carbon component. It is contemplated that oxidation will provide a localized electron density that results in a well-defined paramagnetic M-field distribution along bonds involved in singular and dual chemical bonding with carbon, but at the same time does not introduce chemical contamination to the functionalized carbon material. Without wishing to be bound by theory, oxygen stably and covalently bond with carbon on the atomic level as the electron density distribution and equalization are limited by the structural regularity of carbon matrix.

[021] As shown in Figure 1, in an aspect of the present disclosure, the second carbon component comprises highly organized single-walled carbon nanotubes with dendrite carbon branching toward the exterior of the single-wailed carbon nanotubes. These dendrite carbon branches may be oxidized without detaching from the carbon nanotube. In an aspect, the second component is a multilayer or multi walled carbon nanotube. In such aspects, the individual layers or walls of the carbon nanotube formed (for example, in a pattern of imaginary vertical pyramid) can be oxidized prior to formation of the functionalized carbon material,

[022] In this process, oxygenation of the carbon rings (hexagonal symmetry) may take place on free "floating" dendrite branched carbon substructures and a high concentration of free oxygen ions may permit an electron density equalization process. These carbon nanotubes are very stable chemical materials which can undergo self-assembly resulting in a variety of morphologies: tubes (a), spirals (b), and nanospheres. In an aspect, the second carbon component comprises a carbon nanoparticle having a reduced core-shell symmetry.

[023] The carbon functionalized materials of the present disclosure may find utility as selective adsorbents in a wide variety of applications. In an aspect, the carbon functionalized materials of the present disclosure find utility in the selective adsorption of biological molecules. In another aspect, the carbon functionalized materials of the present disclosure find utility in the selective adsorption of radiation such as electromagnetic radiation. In an aspect, the functionalized carbon materials of the present disclosure are radar-absorbing materials.

[024] The following enumerated aspects are provided as non-limiting examples: A first aspect which is an activated carbon particle having a surface comprising a hydrophobic portion and a hydrophilic portion wherein the hydrophilic portion contains at least one carbon nanoparticle extending away from the surface of the activated carbon particle.

[025] A second aspect which is the particle of the second aspect wherein the at least carbon nanoparticle is associated with the carbon particle via carbon -carbon covalent bonding,

[026] A third aspect which is the particle of any of the first through second aspects having an electrical charge.

[027] A fourth aspect which is the particle of any of the first through third aspects having a wettability in any protic solvent.

[028] A fifth aspect which is the particle of any of the first through fourth aspects wherein the at least one carbon nanoparticle comprises a single layered graphene and a single layered graphene oxide staicture.

[029] A sixth aspect which is the particle of any of the first through fifth aspects wherein the at least one carbon nanoparticle comprises a single walled carbon nanotube.

[030] A seventh aspect which is the particle of any of the first through sixth aspects wherein the at least one carbon nanoparticle has a quarternary structure comprising a ribbon in 3D morphological arrangements.

[031] An eighth aspect which is the particle of any of the first through seventh aspects wherein the at least one carbon nanoparticle extends a distance of from about 1 nm to about 100 micrometers from the carbon particle surface.

[032] A ninth aspect which is a method of preparing a carbon composition comprising contacting an activated carbon bead composition with graphene nanoparticles using graphene-containing electrically conductive electrode, a DC voltage power supply with an applied voltage of greater than about 1.28 VDC, an aprotic electrolyte with DC electrical resistance less than about 18 Ohm/cm.

[033] A tenth aspect which is the method of the ninth aspect wherein the activated carbon bead composition has a bimodal particle size distribution.

[034] An eleventh aspect which is the method of the tenth aspect wherein the bimodal particle size distribution comprises a first particle size ranging from about 10 μηι to about 125 μηι and a second particle size ranging from about 250 μηι to about 500 μηι, [035] A twelfth aspect which is the method of any of the ninth through eleventh aspect wherein the activated carbon bead composition has a trimodal particle size distribution.

[036] A thirteenth aspect which is the method of the twelfth aspect wherein the trimodal particle size distribution comprises a first particle size of from about 10 μηι to about 150 μηι, a second particle size ranging from about 175 μτη to about 500 μηι, and a third particle size ranging from about 500 μη to about 1000 μη .

[037] A fourteenth aspect which is a composition comprising active carbon particle having an electrically charged moiety attached to the surface of the active carbon particles wherein the active carbon particles have a porosity within 5% of a porosity of otherwise similar active carbon particles without an attached electrically charged moiety.

[038] A fifteenth aspect which is a method comprising electrochemical deposition of carbon nanostmcture on to a surface of an activated carbon particle to generate a hydrophilic activated carbon particle.

[039] A sixteenth aspect which is the method of the fifteenth aspect further comprising contacting the hydrophilic activated carbon particle with a biological fluid.

[040] A seventeenth aspect which is the method of the sixteenth aspect wherein the biological fluid comprises plasma and/or whole blood.

[041] An eighteenth aspect which is the method of the seventeenth aspect wherein the contacting of plasma and/or whole blood decreases thrombus formation.

[042] A nineteenth aspect which is the method of any of the fifteenth through nineteenth aspects further comprising contacting the hydrophilic activated carbon particle with at least one biomoiecule.

[043] A twentieth aspect which is the method of the nineteenth aspect wherein the biomoiecule comprises a biochemical radical, an amino acid, a protein, a polysaccharide, a cytokine, a chemokine, or combinations thereof.

[044] A twenty-first aspect which is the method of any of the nineteenth through twentieth aspect wherein the biomoiecule comprises T F-alpha, Activin A, Activin B IL-6 family members, EGF, IL-2 family members, or combinations thereof.

[045] A twenty-second aspect which is a composition comprising an activated carbon particle having a surface comprising a hydrophobic portion and a hydrophilic portion wherein the hydrophilic portion contains at least one carbon nanoparticle extending away from the suiface of the activated carbon particle and wherein the nanoparticle has an electrical charge.

[046] A twenty-third aspect which is a radar absorbing material comprising active carbon particles having an electrically charged moiety attached to the surface of the active carbon particles wherein the electrically charged moiety

[047] A twenty-fourth aspect which is the material of the twenty-third aspect wherein the electrically charged moiety comprises a carbon nanostructure.

[048] A twenty-fifth aspect which is the material of the twenty-fourth aspect wherein the carbon nanostructure has any suitable geometry.

[049] A twenty-sixth aspect which is the material of the twenty-fifth aspect wherein nanostructure has a reduced symmetry core-shell geometry selected from the group consisting of nanoeggs, nanoonions, and nanocups.

[050] A twenty-seventh aspect which is the material of the twenty-fifth aspect wherein the attachment is a carbon-carbon covalent bond.

[051] A twenty-eighth aspect which is the material of any of the twenty-third through twenty- seventh aspects wherein the electrical charge is in the form of zeta potential and dipole momentum.

[052] A twenty-ninth aspect which is a method of preparing a carbon composition comprising

(a) functionalizing a carbon nanostructure to generate a functionalized carbon nanostructure; and

(b) electrochemically attaching the functionalized carbon nanostructure to an activated carbon bead to generate a functionalized activated carbon bead having an electrical charge.

[053] A thirtieth aspect which is a composition prepared according to the method of the twenty- ninth aspect.

[054] A thirty-first aspect which is a radar absorbing materi al comprising the carbon compositi on of the thirtieth aspect.

[055] A thirty-second aspect which is a high temperature coating comprising the composition of the twenty-ninth aspect.

[056] A thirty-third aspect which is a method of making a material resistant to detection by radar comprising coating the material with the coating of the thirty-first aspect.

Claims

1. An activated carbon particle having a surface comprising a hydrophobic portion and a hydrophilic portion wherein the hydrophilic portion contains at least one carbon nanoparticle extending away from the surface of the activated carbon particle.

2. The activated carbon particle of claim 1 wherein the at least carbon nanoparticle is associated with the carbon particle via carbon-carbon covaient bonding.

3. The activated carbon particle of claim 1 having an electrical charge.

4. The activated carbon particle of claim 1 having a wettability in any protic solvent

5. The activated carbon particle of claim 1 wherein the at least one carbon nanoparticle comprises a single layered graphene and a single layered graphene oxide structure.

6. The activated carbon particle of claim 1 wherein the at least one carbon nanoparticle comprises a single walled carbon nanotube.

7. The activated carbon particle of claim 1 wherein the at least one carbon nanoparticle has a quartern ary structure comprising a ribbon in 3D morphological arrangements.

8. The activated carbon particle of claim 1 wherein the at least one carbon nanoparticle extends a distance of from about 1 nm to about 100 micrometers from the carbon particle surface.

9. A method of preparing a carbon composition comprising contacting an activated carbon bead composition with graphene nanoparticles using graphene-containing electrically conductive electrode, a DC voltage power supply with an applied voltage of greater than about 1.28 VDC, an aprotic electrolyte with DC electrical resistance less than about 18 Ohm/cm.

10. The method of claim 9 wherein the activated carbon bead composition has a bimodal particle size distribution.

11. The method of claim 10 wherein the bimodal particle size distribution comprises a first particle size ranging from about 10 μηι to about 125 μτη and a second particle size ranging from about 250 μη to about 500 μηι.

12. The method of claim 9 wherein the activated carbon bead composition has a trimodai particle size distribution.

13. The method of claim 12 wherein the trimodai particle size distribution comprises a first particle size of from about 10 μηι to about 1 50 μηι, a second particle size ranging from about 1 75 μιη to about 500 μη , and a third particle size ranging from about 500 μιη to about 1000 μηι.

14. A composition comprising active carbon particle having an electrically charged moiety attached to the surface of the active carbon particles wherein the active carbon particles have a porosity within 5% of a porosity of otherwise similar active carbon particles without an attached electrically charged moiety.

15. A method comprising electrochemical deposition of carbon nanostructure on to a surface of an activated carbon particle to generate a hydrophiHe activated carbon particle.

16. The method of claim 15 further comprising contacting the hydrophilic activated carbon particle with a biological fluid. 7. The method of claim 16 wherein the biological fluid comprises plasma and/or whole blood.

18. The method of claim 17 wherein the contacting of plasma and/or whole blood decreases thrombus formation.

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19. The method of claim 15 further comprising contacting the hydrophific activated carbon particle with at least one biomolecuie.

20. The method of claim 19 wherein the biomolecuie comprises a biochemical radical, an amino acid, a protein, a polysaccharide, a cytokine, a chemokine, or combinations thereof.

21 . The method of claim 19 wherein the biomolecuie comprises TNF-alpha, Activin A, Activin B JL-6 family members, EGF, JL-2 family members, or combinations thereof.

22. A coating comprising an activated carbon particle having a surface comprising a hydrophobic portion and a hydrophiiic portion wherein the hydrophilic portion contains at least one carbon nanoparticle extending away from the surface of the activated carbon particle and wherein the nanoparticle has an electrical charge.

23. A radar absorbing material comprising active carbon particles having an electrically charged moiety attached to the surface of the active carbon particles wherein the electrically charged moiety,

24. The radar absorbing material of claim 23 wherein the electrically charged moiety comprises a carbon nanostructure.

25. The radar absorbing material of claim 24 wherein the carbon nanostructure has any suitable geometry.

26. The radar absorbing material of claim 25 carbon nanostructure has a reduced symmetry core-shell geometry selected from the group consisting of nanoeggs, nanoonions, and nanocups.

27. The radar absorbing material of claim 23 wherein the attachment is a carbon covalent bond.

28. The radar absorbing material of claim 23 wherein the electrical charge is in the form of zeta potential and dipole momentum.

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29. A method of preparing a carbon composition comprising:

(b) electrochemically attaching the functionahzed carbon nanostructure to an activated carbon bead to generate a functionalized activated carbon bead having an electrical charge,

30. A carbon composition prepared according to the method of claim 29.

31. A radar absorbing material comprising the carbon composition of claim 30.

32. A high temperature coating comprising the composition of claim 29.

33. A method of making a material resistant to detection by radar comprising coating the material with the coating of claim 31.