Magnetic carbon nanomaterial and preparation method thereof

Abstract

Embodiments of the present disclosure relate to methods and apparatus for producing a magnetic carbon nanomaterial product, which may include carbon nanotubes (CNTs), at least some of which are magnetic CNTs (mCNTs). The method and apparatus employ carbon dioxide (CO2) as a reactant in an electrolytic reaction to prepare mCNT. In some embodiments of the present disclosure, a magnetic additive component is included as a reactant in a process and as part of one or more components in a system or composition, thereby facilitating a magnetic material addition process, a carbide nucleation process, or both during an electrosynthesis reaction used to make the magnetic carbon nanomaterial.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Patent Application Serial No. 63 / 022,284, filed on May 8, 2020, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure generally relates to the production of carbon nanomaterials. Specifically, the present disclosure relates to methods, systems and compositions for producing magnetic carbon nanomaterials. Background Art

[0004] Multi-walled carbon nanotubes (CNTs) consist of concentric walls of cylindrical graphene sheets. Graphene is a two-dimensional, honeycomb-structured material consisting of a single layer of sp 2 Hybrid orbital carbon atoms form, which corresponds to the thickness of one carbon atom. CNT has the highest measured tensile strength of any material (strength 93,900MPa). CNT has a variety of useful properties, including high electrical-conductivity, high-thermal conductivity, flexibility, and they can also be chemically modified. The significance of these useful properties is that CNT has a steady increase in their applications.

[0005] A known method of producing CNTs is chemical vapor deposition, CVD. CVD of CNTs is expensive and has a high carbon footprint. Summary of the invention

[0006] Embodiments of the present disclosure relate to methods, systems, and compositions for producing electrosynthesized carbon nanomaterial (CNM) products comprising a variety of nanostructures, including carbon nanotubes (CNTs), at least some of which are magnetic CNTs (mCNTs) or other magnetic carbon nanostructures or morphologies. The methods and apparatus may employ carbon dioxide (CO2) as a carbon source, wherein carbon is a reactant in an electrolysis reaction to prepare a magnetic CNM (mCNM) product that may include mCNTs. The electrolysis reaction causes mass transfer of carbon from the carbon source to the mCNM. In some embodiments of the present disclosure, iron is included as a reactant in the method and as part of one or more components in the apparatus, thereby promoting a magnetic material addition process or a carbide nucleation process or both during an electrolysis reaction for preparing an mCNM product including mCNTs containing iron or iron carbide. In other embodiments of the present disclosure, nickel or nickel carbide is included as a reactant in the method and as part of one or more components in the apparatus, thereby promoting the magnetic material addition process or the carbide nucleation process or both during the electrolytic reaction for preparing an mCNM product including mCNTs containing nickel or nickel carbide.

[0007] Some embodiments of the present disclosure relate to a method for preparing an mCNM product. The method includes the steps of heating an electrolyte medium to obtain a molten electrolyte medium. Then, the molten electrolyte medium is placed between an anode and a cathode of an electrolytic cell. The method also includes the step of placing a magnetic additive component in the electrolytic cell. The method also includes the step of applying an electric current to the cathode and anode in the electrolytic cell and the step of collecting the mCNM product from the cathode.

[0008] Some embodiments of the present disclosure relate to methods for selecting properties of one or more specific structures / morphologies of mCNM products. mCNM products can be affected by a magnetic field in terms of their position and / or their orientation. Without being bound by any particular theory, mCNM products can be used for: one or more medical applications, such as drug delivery and imaging; for accurate positioning; consumer electronic devices; information storage; wastewater treatment; electrochemical sensors; and / or as catalysts in a variety of chemical reactions.

[0009] As used herein, the term "selecting the morphology of nanomaterials" refers to any step that helps control the structure and / or morphology of the electrosynthesized mCNM product. In some embodiments of the present disclosure, the morphology of the selected mCNM may include the following CNM morphologies: carbon nanotubes, carbon nanofibers, carbon nanoonions, carbon nanoscaffolds, carbon nanospheres, carbon nanohelices, carbon nanosheets, graphene, or combinations thereof. In some embodiments of the present disclosure, the step of selecting the morphology of nanomaterials may result in the electrosynthesis of mCNM products of a partial, majority, substantially all, or all single CNM morphology. For example, in terms of current and / or chemical components, the step of selecting the morphology of nanomaterials may include adding a nanomaterial selection component for producing an electrosynthesized mCNM product in one of the following morphologies: mCNTs, magnetic carbon nanofibers, magnetic carbon nanoonions, magnetic carbon nanoscaffolds, magnetic carbon nanospheres, magnetic carbon nanohelices, magnetic carbon nanosheets, or magnetic graphene.

[0010] In some embodiments of the present disclosure, the step of selecting the nanomaterial morphology comprises applying the current to the cathode and the anode as a direct current (DC). For example, a DC electrolysis current can be selected for mCNM products comprising CNT morphology.

[0011] In some embodiments of the present disclosure, the step of selecting the nanomaterial morphology comprises applying the current to the cathode and the anode as an alternating current (AC). For example, the AC electrolysis current can be selected for CNM products having a nano-onion morphology.

[0012] In another embodiment, the step of selecting the nanomaterial morphology comprises adding ZnO to a molten electrolyte medium and applying an AC electrolysis current, which may select for a CNM product having a graphene sheet morphology.

[0013] In another embodiment, the step of selecting the nanomaterial morphology comprises adding iron oxide to the electrolyte medium and selecting a high density current for the carbon nanohelix product.

[0014] In another embodiment, the step of selecting the nanomaterial morphology comprises adding MgO to the molten electrolyte medium and selecting an electric current for the production of hollow carbon nanospheres.

[0015] Some embodiments of the present disclosure relate to a system including an electrolytic cell for preparing one or more magnetic carbon nanomaterial products. The electrolytic cell includes one or more walls defining a plenum and an anode and a cathode positioned within the plenum. The plenum is configured to receive and maintain a molten electrolyte medium between the anode and the cathode. The electrolytic cell is further configured to receive a magnetic material addition component or a carbide growth component, an optional nanomaterial selection component, and an electric current applied to the anode and the cathode to cause an electrolytic reaction for preparing one or more magnetic carbon nanomaterial products.

[0016] Without being bound by any particular theory, embodiments of the present disclosure relate to an electrolytic reaction of cracking carbon dioxide (CO2) in a molten electrolyte medium to produce mCNM products, including carbon nanotubes (mCNTs), by a magnetic material addition process or a carbide nucleation process or both. Magnetic carbon nanomaterials, including mCNTs, have a variety of applications, such as directing therapy to a localized area of ​​a subject in medical therapy. Magnetic carbon nanomaterials, including mCNTs, can also be used as retrievable catalysts.

[0017] Other embodiments of the present disclosure relate to electrosynthetic methods for preparing mCNM products in the absence of CO2. Without being bound by any particular theory, some embodiments of the present disclosure relate to an electrolytic reaction in which carbonates are cracked in a molten electrolyte medium to provide a carbon source for preparing mCNM products, including carbon nanotubes (mCNTs), by a magnetic material addition process or a carbide nucleation process or both.

[0018] Some embodiments of the present disclosure relate to the use of a container made of a material containing iron and / or nickel to receive and maintain a molten electrolyte medium. In addition or as an alternative, the iron and / or nickel from the anode can migrate to the cathode on which the carbon nanotubes are grown. For example, energy dispersive X-ray spectroscopy (EDS) elemental analysis confirms the presence of iron in the carbon nanotubes, and X-ray diffraction (XRD) analysis confirms the presence of iron carbide. An iron-containing container can be used, an iron-rich alloy such as Incoloy is used for the anode, an iron-containing alloy is used for the cathode, and an excess of iron in the electrolyte medium is achieved by providing a further iron source through an iron-based additive that can be introduced into the electrolyte medium, the electrolyte medium itself, or a combination thereof. Excessive iron, rather than a nucleation facilitator, can result in the addition of magnetic materials on the outer surface of the structure in the mCNT product, such as a graphene layer, also referred to as graphite carbon, a coating of iron carbide nodules, and in mCNM, such as mCNT structure, resulting in iron carbide.

[0019] Some embodiments of the present disclosure relate to a composition as an electrolyte medium for preparing a magnetic carbon nanomaterial product. The electrolyte medium comprises a carbonate; and a magnetic material addition component or a carbide growth component or both.

[0020] Without being bound by any particular theory, embodiments of the present disclosure may reduce the greenhouse gas footprint of methods and systems for preparing mCNM products that may include mCNTs and / or other magnetic nanostructures by using CO2 from the atmosphere or from anthropogenic sources as a carbon source to provide carbon as a reactant in the electrolysis reactions of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] These and other features of the present disclosure will become more apparent from the following detailed description, which proceeds with reference to the accompanying drawings.

[0022] Figure 1 shows two photographs and a line graph, where Figure 1A is a photograph of an electrolysis cell according to an embodiment of the present disclosure; Figure 1B is a line graph showing the concentration (%) of electrolysis gas output collected from the head space of an electrolytic cell over time (hours) during an electrolysis reaction in Li2CO3 at about 770°C, wherein line Y1 shows the concentration of carbon dioxide without Li2O, line Z1 is oxygen without Li2O, line Y2 shows carbon dioxide using 1 m Li2O and line Z2 shows oxygen using 1 m Li2O; and Figure 1C is a photograph of a carbon nanomaterial product attracted to a magnet according to an embodiment of the present disclosure.

[0023] FIG. 2 shows three images and a line graph of carbon nanomaterial products according to embodiments of the present disclosure, wherein Figure 2A is a scanning electron microscope (SEM) image of the carbon nanomaterial product (scale bar is 50 μm); Figure 2B is a transmission electron microscope (TEM) image of the carbon nanomaterial product (scale bar is 200 nm); Figure 2C is greater than Figure 2C Another TEM image of the carbon nanomaterial product at a magnification of the image (scale bar is 2 nm); and Figure 2D Is the display edge Figure 2C Line 2C in FIG. 2 is a line graph of the spacing between the walls of 10 carbon nanotubes in the carbon nanomaterial product.

[0024] FIG. 3 shows a SEM image of a carbon nanomaterial product according to an embodiment of the present disclosure, wherein Figure 3A is the SEM image at the first magnification (scale bar is 200 μm); Figure 3B is a SEM image at a second, higher magnification (scale bar, 10 μm); Figure 3C is another SEM image at the third magnification (scale bar is 10 μm); Figure 3D is a high-resolution SEM image at a first magnification (scale bar is 3 μm); and Figure 3E is a high-resolution SEM image at a second, higher magnification (scale bar 1 μm).

[0025] FIG4 shows the X-ray diffraction (XRD) analysis results of the carbon nanomaterial product prepared according to an embodiment of the present disclosure, wherein Figure 4A shows an XRD analysis when the electrolyte medium used in the production process is melted about 1 day before initiating the electrolysis step; Figure 4B shows an XRD analysis when the electrolyte medium used in the production method is freshly melted; and Figure 4C A library XRD of carbon nanomaterial product related compounds is shown.

[0026] FIG. 5 shows the energy dispersive X-ray spectra (EDS) of three carbon nanomaterial product spots prepared according to an embodiment of the present disclosure when the electrolyte medium used in the production method is melted about 1 day before initiating the electrolysis step, wherein Figure 5A Data obtained at the first position within the product are shown; Figure 5B showing data obtained at a second location within the product; and Figure 5C Data obtained at a third position within the product are shown.

[0027] Figure 6EDS elemental analysis data is shown, including: the top row shows bright field (BF), dark field (DF), and high angle annular dark field (HAADF) images of a high-resolution TEM acquired at a first magnification (scale bar is 500 nm) from a first zone (inside the rectangle added to the image) of a carbon nanomaterial product prepared according to an embodiment of the present disclosure; the middle row shows BF, DF, and HAADF images of a TEM acquired at a second, larger magnification (scale bar is 50 nm) from a first zone of a carbon nanomaterial product prepared according to an embodiment of the present disclosure; and the bottom row shows the presence / absence of carbon (left image), iron (middle image), and nickel (right image).

[0028] Figure 7 EDS elemental analysis data is shown, including: the top row shows bright field (BF), dark field (DF), and high angle annular dark field (HAADF) images of a high-resolution TEM acquired at a first magnification (scale bar is 500 nm) from a second region (inside the rectangle added to the image) of a carbon nanomaterial product prepared according to an embodiment of the present disclosure; the middle row shows BF, DF, and HAADF images of a TEM acquired at a second, larger magnification (scale bar is 50 nm) from a first region of a carbon nanomaterial product prepared according to an embodiment of the present disclosure; and the bottom row shows the presence / absence of carbon (left image), iron (middle image), and nickel (right image).

[0029] FIG. 8 shows an image of mCNTs formed according to an embodiment of the present disclosure, wherein Fig. 8A , Figure 8B and Figure 8C SEM images of CNT products formed by cracking carbon dioxide (CO2) in a molten electrolyte medium are shown at different magnification levels; and Fig.8D , Fig. 8E and Figure 8F TEM images of CNT products formed by cracking CO2 in a molten electrolyte medium are shown at different magnification levels.

[0030] FIG9 shows an image of the product of CNT formation in a cast iron container with a brass cathode and a nickel-chromium alloy anode, where Fig.9A (i) shows a container, Fig.9A (ii) shows a side view of the cathode and anode with CNT products thereon; Fig.9A (iii) shows a front view of a cathode with CNT product thereon; Fig. 9B An SEM image of the CNT product after dissociation from the cathode is shown at a first magnification; Fig. 9C Shown at a second, higher magnification Fig. 9BCNT products; Fig.9D Shown at a third, greater magnification Fig. 9C CNT products; Fig.9E At a fourth, greater magnification, Fig.9D CNT products; and Fig.9F At a fifth, greater magnification, Fig.9E CNT products. DETAILED DESCRIPTION

[0031] Embodiments of the present disclosure relate to methods, systems, and compositions for producing magnetic carbon nanomaterial (mCNM) products comprising carbon nanostructures, at least some of which are magnetic. At least one example of a magnetic carbon nanostructure is a magnetic carbon nanotube (mCNT). As used herein, the terms "magnetic carbon nanomaterial," "magnetic carbon nanostructure," "magnetic carbon nanotube," and "mCNT" generally or specifically refer to carbon nanomaterials that contain iron, iron carbide, nickel, nickel carbide, or other magnetic materials to the extent that the carbon nanomaterial can move through a magnetic field, as defined below, whenever the context permits. The methods and apparatus use carbon dioxide (CO2) as a reactant in an electrolytic reaction to prepare an mCNM product. In some embodiments of the present disclosure, iron, nickel, or other magnetic materials are included as reactants in the method and as part of one or more components in the system, thereby assisting the magnetic material addition process or the carbide nucleation process, or both, during the electrolytic reaction to prepare the mCNM product.

[0032] Some embodiments of the present disclosure relate to methods for preparing mCNM products using an electrolytic reaction. The electrolytic reaction occurs in an environment where a molten electrolyte medium is positioned between an anode and a cathode. Carbon is introduced into the molten electrolyte medium as pure CO2, anthropogenic CO2, such as CO2 from a chimney or combustion exhaust, concentrated CO2, or CO2 entrained in atmospheric air. In addition, iron is present in the environment. The iron can be derived from the material constituting one or more walls of the electrolytic cell in which the electrolytic reaction occurs, from the anode, from the cathode, from additives added to the electrolyte medium, or a combination thereof. When an electric current having a substantially constant current density is applied to the anode and the cathode, the CO2 is cracked to produce carbon, which is combined with iron to form an mCNM product. As will be appreciated by those skilled in the art, other magnetic materials, such as nickel, can also be combined with the produced carbon to prepare an mCNM product.

[0033] Unlike the known chemical vapor deposition (CVD) method for preparing CNTs, the physicochemical environment of the embodiments of the present disclosure is an electrochemical method, while CVD is a chemical method. The embodiments of the present disclosure use CO2 as a reactant, while CVD uses organic reactants. The embodiments of the present disclosure use a chemical reaction to construct mCNM products at the interface between a molten electrolyte medium and a solid cathode, while CVD typically occurs at a gas / solid interface.

[0034] There are other subtle differences between the embodiments of the present disclosure and the CVD method. The embodiments of the present disclosure provide a higher density of reactive carbon (molten electrolyte medium) on the cathode near the growth interface. Although the CVD may or may not apply an electric field to the substrate during the CVD method, the embodiments of the present disclosure always apply a strong electric field that rapidly decreases through the double layer near the cathode during the growth of the mCNM product. CVD has been associated with transition metal nucleation of carbon to grow CNTs. The ability of carbides to dissolve carbon, and thereby nucleation growth of CNTs or mCNTs, has not been previously considered to be suitable for the electrochemical environment of the embodiments of the present disclosure.

[0035] Carbon nanomaterials containing iron carbide or other ferromagnetic magnetic materials, referred to herein as magnetic carbon nanomaterials, are attracted to magnets, and are of increasing interest in a wide range of fields, including medicine and catalysis. Known magnetic materials include, but are not limited to, iron, nickel, cobalt, gadolinium, samarium, neodymium, and alloys containing one or more of these magnetic materials, such as steel, as well as materials with significant, but lesser, ferromagnetism, paramagnetism, or diamagnetic properties. Each of these magnetic materials may be referred to herein as a "magnetic additive component" and it is considered that they are within the embodiments of the present disclosure, and any other material that can aid in the formation of mCNMs by electrosynthesis methods is also considered within the embodiments of the present disclosure. mCNM products have a variety of uses in medical applications, such as as tools for targeted drug delivery and imaging, in imaging, such as magnetic resonance imaging (MRI), stem cells, and anticancer agents for the treatment of colon cancer, lymphoma, melanoma, and bladder cancer.

[0036] For catalyst applications, the field of magnetic and therefore retrievable nanoscale and dendritic materials has been investigated and is gaining increasing interest. Specific applications include mCNTs, magnetic graphene and magnetic carbon spheres and nano-onion catalysts.

[0037] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0038] As used herein, the term "about" refers to a deviation of approximately + / - 10% from a given value. It should be understood that these variations are always included in any given value provided herein, whether or not specifically mentioned.

[0039] As used herein, the term "magnetic" refers to a property of a material that can be affected by a magnetic field, or that it can generate a magnetic field. When a material is affected by a magnetic field, it can change its orientation to align with the magnetic field lines of the magnetic field, and / or it can move in response to the presence of a magnetic field.

[0040] As used herein, the term "magnetic additive component" refers to a chemical component that can participate in the electrosynthesis method of the present disclosure to prepare an mCNM product. The magnetic additive component can be a magnetic material addition component or a carbide growth component or a combination thereof that can be used in the methods, systems and as part of the composition of the present disclosure, thereby introducing or forming a magnetic material and / or carbide on top of, inside, or both of the carbon nanoscale structure that is a component of the mCNM product. The term "magnetic material addition component" can be used herein to represent a chemical component that contains a magnetic material and can participate in the preparation of an mCNM product by a magnetic material addition process. The term "carbide growth component" can be used herein to represent a carbide chemical component that can participate in the preparation of an mCNM product by a carbide nucleation process. Typically, a magnetic additive component is introduced into the mCNM product so that one or more constituent nanostructures within the mCNM product are movable when placed in or near a magnetic field.

[0041] Embodiments of the present disclosure will now be described with reference to examples and drawings.

[0042] Some embodiments of the present disclosure relate to methods for producing mCNM products that may contain mCNTs. The method includes the following steps: heating an electrolyte medium to obtain a molten electrolyte medium; positioning the molten electrolyte medium between the anode and cathode of an electrolytic cell; positioning a magnetic additive component, such as a material addition component or a carbide growth component, in the electrolytic cell; applying an electric current to the cathode and anode in the electrolytic cell; and collecting the mCNM product from the cathode. Optionally, the method also includes the step of selecting the mCNM product to contain a greater proportion of a desired nanoscale morphology (which may also be referred to herein as a desired nanostructure).

[0043] As the technical reader will appreciate, the step of heating the electrolyte medium can be achieved in a variety of ways. For example, a heating device, such as an oven or furnace, can be used to heat the electrolyte medium to a sufficient temperature so that it is converted into a molten liquid state. As such, any heating device that can achieve the temperature required to heat the electrolyte medium to its melting temperature is contemplated herein.

[0044] In some embodiments of the present disclosure, the electrolyte medium comprises one or more carbonates. In some embodiments of the present disclosure, the electrolyte medium comprises a lithiated carbonate electrolyte, which includes pure Li2CO3 (melting temperature is about 723°C), or Li2CO3 mixed with other carbonates, such as Na2CO3, K2CO3, MgCO3, CaCO3, BaCO3, or Li2CO3 mixed with other salts, including oxides, borates, sulfates, phosphates or nitrates.

[0045] The molten electrolyte medium is positioned between the anode and cathode of the electrolytic cell. The electrolytic cell can be any type of container that can maintain its structural integrity in the face of the electrochemical environment that occurs during the electrolytic reaction of the present disclosure. The electrolytic cell will have one or more walls that can be made of or coated with a desired material.

[0046] A magnetic additive component refers to a chemical component that may be a component of the electrolyte medium, or that is additionally added to the electrolyte medium before or during the electrosynthesis method disclosed herein. In some embodiments of the present disclosure, the magnetic additive component may be a magnetic material addition component or a carbide growth component, or any combination thereof. The magnetic additive component may be derived from one or more walls of the electrolytic cell. In some embodiments of the present disclosure, the magnetic additive component is derived from the anode. In some embodiments of the present disclosure, the magnetic additive component is derived from the cathode. In some embodiments of the present disclosure, the magnetic additive component is derived from an iron-based additive added to the electrolyte medium. In some embodiments of the present disclosure, the magnetic additive component is derived from the electrolyte medium. In some embodiments of the present disclosure, the magnetic additive component is derived from one or more walls of the electrolytic cell, the anode, the cathode, an iron-based additive added to the electrolyte medium, or any combination of the electrolyte medium.

[0047] The magnetic additive component can be added to the electrolyte medium in a suitable amount. For example, in some embodiments of the present disclosure, the magnetic additive component is added to the electrolyte medium in an amount of about 0.001 molal to about 10 molal or more. In some embodiments of the present disclosure, the magnetic additive component is added to the electrolyte medium in an amount of about 0.003 molal to about 3 molal, in an amount of about 0.01 molal to about 1 molal, or 0.03 molal to about 0.3 molal. As used herein, the term "molal" refers to 1 mole of magnetic additive component per kilogram of electrolyte medium. In other embodiments of the present disclosure, the magnetic additive component is added in an amount of about 0.03 to 0.06 molal, 0.07 to 0.10 molal, 0.03 to 0.05 molal, 0.03 to 0.05 molal, 0.10 to 0.13 molal, 0.14 to 0.17 molal, 0.18 to 0.21 molal, 0.22 to 0.25 molal, 0.26 to 0.30 molal. In a preferred embodiment of the present disclosure, the magnetic additive component is added in an amount of about 0.1 molal.

[0048] In some embodiments of the present disclosure, the electrolyte medium may be melted inside the electrolytic cell, or it may be melted outside the cell and transferred therein. Since the electrolysis reaction may occur within a period of time in which the molten electrolyte medium may cool, the electrolytic cell may be configured with its own integrated heater or it may be configured to be heated by an external heating device located outside the electrolytic cell, thereby maintaining the electrolyte medium in a molten state for a desired period of time. Additionally and without being bound by any particular theory, in the absence of a heater, heat is added by both the exothermic reaction of CO2 and the resistive heat generated by the electrolysis overvoltage.

[0049] In some embodiments of the present disclosure, the electrolytic cell can be configured to maintain the electrolyte medium at least at about 375°C, at least at about 400°C, at least at about 500°C, at least at about 600°C, at about 650°C, at least at about 675°C, at least at about 700°C, at least at about 725°C, at least at about 750°C, at least at about 775°C, at least at about 800°C, at least at about 825°C, at least at about 850°C, at least at about 875°C, at least at about 900°C, or at least at about 1000°C.

[0050] Anode can be made of multiple metals or alloys. Some anodes can be made of materials comprising nickel, chromium, iron or a combination thereof. Some non-limiting examples of materials suitable for the anode of the present disclosure include: substantially pure nickel, alloys substantially mainly composed of nickel, alloys composed of certain nickel, substantially pure chromium, alloys substantially mainly composed of chromium, alloys composed of certain chromium, substantially pure iron, alloys substantially mainly composed of iron, alloys composed of certain iron or a combination thereof. For example, Inconel 718 or other Inconels, such as (but not limited to) Inconel 600 and Inconel 625, NichromeA (composed of about 80% nickel and about 20% chromium), Nichrome C (roughly composed of nickel, iron and chromium), Incoloy alloys (such as Incoloy 800 composed of about 40% iron, about 30-35% nickel and about 19-23% chromium) or a combination thereof can be suitable for use as anodes in embodiments of the present disclosure. The anode may be planar in shape, or other shapes that facilitate molten electrolysis, and may be manufactured in a variety of sizes to fit within an electrolytic cell.

[0051] In some embodiments of the present disclosure, the magnetic additive component may be derived from the anode, and the magnetic additive component may include the anode in an amount of about 0.001 wt % to about 100 wt % of the total material. In some embodiments of the present disclosure, the magnetic material may include the anode in an amount of about 0.01 wt % to about 99 wt % of the total material, about 0.1 wt % to about 90 wt %, or 1 wt % to about 90 wt %, or about 10 wt % to about 50 wt %.

[0052] In other embodiments of the present disclosure, the magnetic additive component is added in an amount of about 0.01 wt% to 19 wt%, 10 wt% to 20 wt%, 10 wt% to 20 wt%, 30 wt% to 40 wt%, 40 wt% to 50 wt%, 50 wt% to 60 wt%, 60 wt% to 70 wt%, 70 wt% to 80 wt%, 90 wt% to 100 wt%. In a preferred embodiment of the present disclosure, the wt% is 30% wt% to about 50 wt%. In other embodiments of the present disclosure, the magnetic additive component in the anode is added to an alloy containing two or more magnetic materials, such as about 80 wt% of one magnetic metal and 20% of another magnetic metal.

[0053] The cathode can be made of a variety of metals or alloys. Some cathodes can be made of materials comprising copper, zinc, iron or a combination thereof. Some non-limiting examples of materials suitable for the cathode of the present disclosure include: substantially pure copper, an alloy consisting essentially of copper, an alloy consisting essentially of certain copper, substantially pure zinc, an alloy consisting essentially of zinc, an alloy consisting essentially of certain zinc, substantially pure iron, an alloy consisting essentially of iron, an alloy consisting essentially of certain chromium, substantially pure iron, an alloy consisting essentially of iron, an alloy consisting essentially of certain iron or a combination thereof. For example, brass, such as Montz brass, can be suitable for use as the cathode in the embodiments of the present disclosure. The shape of the cathode can be a plane, or other shapes that contribute to molten electrolysis, and can be prepared into a variety of sizes to fit in an electrolytic cell.

[0054] The magnetic additive component may be derived from the cathode, and the magnetic additive component may include the cathode in an amount of about 0.001wt% to about 100wt% of the total material. In some embodiments of the present disclosure, the magnetic additive component may include the cathode in an amount of about 0.01wt% to about 99wt% of the total material, about 0.1wt% to about 90wt%, or 1wt% to about 90wt%, or about 10wt% to about 50wt%. In other embodiments of the present disclosure, the magnetic additive component is added to the cathode material in an amount of about 0.01wt% to 19wt%, 10wt% to 20wt%, 30wt% to 40wt%, 40wt% to 50wt%, 50wt% to 60wt%, 60wt% to 70wt%, 70wt% to 80wt%, 90wt% to 100wt%. In a preferred embodiment of the present disclosure, the magnetic additive component is added to the cathode in an amount of 30% to about 50wt% of the total cathode material. In other embodiments of the present disclosure, the magnetic additive component in the cathode is added to an alloy containing two or more magnetic additive components, for example, about 80 wt% of one magnetic additive component and 20% of another magnetic additive component based on the total amount of magnetic additive components in the total cathode material or based on the total cathode material. The step of positioning the magnetic additive component in the electrolytic cell includes adding a magnetic additive component comprising a metal salt and / or a carbide to the electrolytic cell so that when the electrolysis reaction occurs, the magnetic additive component contributes to the growth of the mCNM product. In some embodiments of the present disclosure, the carbide can participate in one or more nucleation reactions that lead to the growth of CNTs and mCNTs in the mCNM product. In some embodiments of the present disclosure, the carbide can be magnetic.

[0055] In some embodiments of the present disclosure, the magnetic additive component may occur as a metal, a metal salt, including but not limited to a metal carbide or a non-metal carbide, or any combination thereof.

[0056] Suitable examples of metal carbides include, but are not limited to, iron carbide, nickel carbide, cobalt carbide, zirconium carbide, chromium carbide, tantalum carbide, hafnium carbide, or any combination thereof.

[0057] Suitable examples of non-metallic carbides include, but are not limited to, silicon carbide, germanium carbide, or any combination thereof.

[0058] In some embodiments of the present disclosure, the current is applied at a substantially constant current density. For example, the current density of the applied current may be about 0.001 A / cm 2 To about 10A / cm 2 In some embodiments, the current density of the applied current can be about 0.003A / cm 2 To about 3A / cm 2 Between; about 0.01A / cm 2 To about 1A / cm 2 Between; about 0.03A / cm 2 To about 0.6A / cm 2 or about 0.06A / cm 2 To about 0.3A / cm 2 In some embodiments of the present disclosure, the current density is about 0.1 A / cm 2 .

[0059] According to Equation 1 (EQN.1), the equilibrium concentration of 0.2 molal lithium oxide in molten Li2CO3 electrolyte at 750°C is:

[0060]

[0061] During CO2 molten carbonate electrolysis, small transition metal "seeds" were observed at the ends of CNT products, and it has been shown that the molten carbonate CNT growth mechanism can be activated by both tip and root transition metal nucleation processes.

[0062] The reduction of CO2 in lithiated carbonate electrolytes is a 4e-process, without being bound by any particular theory, which proceeds according to Equation 2 (EQN.2):

[0063] Li2CO 3(熔融) →C (纳米材料) +O 2(气体) +Li2O (溶解) (EQN.2).

[0064] Without being bound by any particular theory, CO2 added to the molten electrolyte medium chemically reacts with lithium oxide to renew and reform Li2CO3 according to Equation 3 (EQN.3):

[0065]

[0066] Without being bound by any particular theory, according to the 4e-transfer reaction equation 4 (EQN.4), when EQN.2 is combined with EQN.3, this yields a net electrolysis reaction:

[0067] CO 2(气体) →C (纳米材料) +O 2(气体) (EQN.4).

[0068] Lithium carbonate melts at about 723°C. At temperatures above 800°C, without being bound by any particular theory, 2, rather than 4 electron reduction is dominant, and without being bound by any particular theory, according to the 2e-transfer reaction equation 5 (EQN.5), at 950°C, the electrolysis product is pure carbon monoxide, rather than carbon:

[0069] CO 2(气体) +2e - →CO 2(气体) +1 / 2O 2(气体) (EQN.5).

[0070] Example

[0071] Example 1

[0072] To implement the method of the present disclosure, an electrolyte medium is prepared using lithium carbonate (Li2CO3, about 99.5% pure) and lithium oxide (Li2O, about 99.5% pure). Using a heating element, the electrolyte medium is heated until melted to provide a molten electrolyte. The molten electrolyte medium is then positioned in an electrolytic cell including one or more walls for defining a gas collecting chamber between them. As further discussed below, the walls of the electrolytic cell are composed of (or coated with) stainless steel, such as stainless steel 304, or cast iron. Within the electrolytic cell, an anode and a cathode are positioned. The anode is made of Inconel 718. During electrolytic operation, the anode can be selected to produce oxygen. The cathode is composed of Mont Blanc, which is an alloy of about 59-61% copper and about 39-41% zinc and some trace amounts of iron.

[0073] When the molten electrolyte medium is positioned within the electrolytic cell and between the anode and cathode, an electric current is applied to the anode and cathode to initiate the electrolysis reaction. In this example, the current is about 0.5 amperes (A) and is applied at a constant current density.

[0074] During the electrolytic reaction, the carbon nanomaterial product is collected on the cathode. When the electrolytic reaction stops, the cathode is removed from the electrolytic cell by removing the current and allowed to cool. The carbon nanomaterial product can then be collected from the cooled cathode by tapping. The carbon nanomaterial product is then washed with deionized water (DI water) or up to 6 molar hydrochloric acid. It was observed that both types of washing resulted in similar carbon nanomaterial products, but acid washing accelerated the washing. The washed carbon nanomaterial product is then separated from the washing solution by paper filtration or centrifugation. It was observed that both separation methods resulted in similar carbon nanomaterial products, but the use of centrifugation accelerated the separation step.

[0075] Figure 1A A photograph of an example of a stainless steel 304 electrolytic cell for producing carbon nanomaterial products according to an embodiment of the present disclosure is shown. Pure CO2 was bubbled into a molten lithium carbonate electrolyte with and without lithium oxide (1 mol Li2O / kg Li2CO3). Figure 1B As shown, after a short period of activation, the gas phase portion of the electrolysis reaction product is increased to about 100% oxygen and no CO2 escapes from the electrolysis reaction. Figure 1A The electrolysis was carried out in a stainless steel 304 electrolytic cell. Within the electrolytic cell, the anode was made of Inconel 718 and the cathode was made of Monts brass. During the electrolytic reaction, in accordance with EQN.4 above, a carbon nanomaterial product grew on the cathode and after cooling and cleaning, the carbon nanomaterial was found to be carbon nanotubes. The extracted cathode was cooled and the solid product was easily stripped from the cathode and cleaned to remove any excess electrolyte medium. Unexpectedly, when the electrolytic reaction was carried out in an electrolytic cell having at least some iron in the walls of the cell, the carbon nanomaterial product was found to be magnetic. Figure 1C As shown, magnetic CNTs are strongly attracted to magnets.

[0076] Example 2

[0077] This example uses many of the same steps as Example 1, with one exception being that CO2 in air (about 216 ppm CO2 in ambient air), rather than pure CO2 or concentrated CO2 from air, is introduced and bubbled into the molten electrolyte medium. In this example, the electrolyte medium used is a molten Li2CO3 electrolyte medium that has been exposed to hot air for about 24 hours before initiating the electrolysis reaction by applying an electric current similar to the other examples described herein. The anode is about 5 cm 2 The cathode is made of Inconel 718 plate, and the cathode is made of Monz brass plate. The carbon nanomaterial produced in this example is also magnetic.

[0078] To characterize the crystal structure of the carbon nanomaterial product, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to image the product. X-ray diffraction (XRD) was used to characterize the atomic structure of the carbon nanomaterial product.

[0079] The carbon nanomaterial product was collected from the cathode, washed and separated, and analyzed by a PHENOM Pro Pro-X scanning electron microscope (SEM) with EDS, a FEI Teneo LV SEM, and by a FEI Teneo Talos F200X transmission electron microscope (TEM). XRD powder diffraction data were collected on a Rigaku Miniflex diffractometer and analyzed by the Jade software package.

[0080] The basic morphology of the carbon nanomaterial products is essentially the same whether they are produced in a ceramic (alumina) or steel cell. An exception is observed when excess iron is introduced from the anode during the electrolysis reaction, as will be shown in the examples that follow.

[0081] Figure 2A is a SEM image showing the highly uniform carbon nanomaterial product, in this case carbon nanotubes (CNTs), using CO2 from air as a reactant. Figure 2A In the figure, the scale bar is 2 nm. Figure 2B and Figure 2C is a TEM image showing CNT walls, and the graphene spacing between CNT walls is estimated to be 0.33 to 0.34 nm (see, Figure 2D The distance between the two red bars and every 10 peaks below the arrows on both sides). Figure 2B The scale bar is 200 nm, and Figure 2C In the figure, the scale bar is 2 nm.

[0082] Example 3

[0083] As part of the carbon nanomaterial product prepared according to embodiments of the present disclosure, other magnetic CNTs were prepared. In this example, magnetic CNTs were prepared when the anode did not contain iron.

[0084] The electrolysis reaction is carried out using one or more electrolytic cells whose walls are lined with nickel or a nickel alloy to reduce the presence of iron in the electrolytic cell. The electrolyte medium is molten Li2CO3 containing about 0.67m Li2O (about 2% by weight compared to the weight of the entire electrolyte medium) and is maintained at a temperature of about 770°C. The electrolytic cell is open to air containing CO2. The anode is made of Nichrome A and the cathode is made of Monts brass. The electrolyte is heated to about 0.1A / cm 2The electrolysis reaction takes place at a substantially constant current density of 25 A.

[0085] After about 4 hours of electrolysis, the cathode was removed from the electrolytic cell and cooled. The solid carbon nanomaterial product was stripped from the cathode and washed to remove excess electrolyte medium prior to microscopy.

[0086] The carbon nanomaterial product was found to be about 98% uniform CNTs, as determined by multiple SEM and TEM visual inspections. During the electrolysis reaction, the coulombic efficiency reached 100%. The coulombic efficiency of the electrolysis was calculated as the percentage of the applied constant current charge converted to carbon, as determined by the following equation 6 (EQN.6):

[0087] 100% × C 实验 / C 理论 (EQN.6).

[0088] This is the mass of the cleaned carbon product removed from the cathode (C 实验 ) measured, and according to the theoretical mass C 理论 =(Q / nF)×(12.01 g C mol -1 ) is calculated, the theoretical mass is determined from Q, F, and n, Q is the time-integrated charge passed during electrolysis, F is the Faraday constant (96485As mol -1 e - ) and n = 4e-mol -1 Reduction of tetravalent carbon.

[0089] Figure 3A , Figure 3B and Figure 3C They are SEM images of the carbon nanomaterial products of Example 3 respectively. Figure 3A With a scale bar of 200 μm, Figure 3B With a scale bar of 10 μm and Figure 3C Scale bar with 10 μm. Figure 3D and Figure 3E High-resolution SEM images with scale bars of 3 μm and 1 μm, respectively.

[0090] Example 4

[0091] As part of the mCNM product prepared according to embodiments of the present disclosure, other magnetic CNTs were prepared. In this example, magnetic CNTs were prepared by two electrolyte medium samples. The first electrolyte medium of sample A was melted for about 1 day before initiating the electrolysis step; the second electrolyte medium used for sample A in the electrolysis was freshly melted.

[0092] The electrolysis reaction was carried out using one or more electrolytic cells whose walls consisted of stainless steel 304. The electrolyte medium was molten Li2CO3 containing about 0.67m Li2O (about 2% by weight compared to the weight of the entire electrolyte medium) and was maintained at a temperature of about 770°C. The electrolytic cell was open to air containing CO2. The anode was made of Nichrome A and the cathode was made of Montz brass. The electrolyte was heated to about 0.1A / cm 2 The electrolysis reaction occurs by applying current at a substantially constant current density of 25A.

[0093] After about 4 hours of electrolysis, the cathode was removed from the electrolytic cell and cooled. The solid carbon nanomaterial product was stripped from the cathode and washed to remove excess electrolyte medium prior to microscopy.

[0094] Figure 4A X-ray diffraction (XRD) results of sample A are shown. Figure 4B The XRD results of sample B are shown. Figure 4C Library XRD of product related compounds (graphitic carbon, iron carbide and nickel or lithium chromium oxide) is shown. The XRD results of sample A show evidence of significantly more iron carbide in the graphitic carbon product compared to the XRD results of sample B. There is no obvious sign of corrosion after either electrolysis reaction, but the long electrolyte medium soaking before sample A resulted in more iron carbide in the product. Specifically, compared with the XRD library, both sample A and sample B show peaks of chromium or nickel oxide at x and z (see Figure 4A and Figure 4B ), and both samples show the peak of graphite at y. However, compared with sample B, the ratio of the peaks in sample A, i.e. the relative height of peak z to peak x or y shows the strong contribution of iron carbide spectrum at y and z. In addition, there is a double peak at about 44 °, and in sample A, compared with the right side peak or peak x, the advantage of the left side peak is consistent with the contribution of iron carbide. The EDS of sample A is consistent with the XRD result of sample A, which shows the elemental analysis at 3 points on the carbon nanomaterial product, i.e. the point of C of 100.0% atomic percentage, the point of 94.9% C and 5.1% Fe and the point of 92.4% C, 5.8% Fe and 1.9% Cr. Although the source of the iron forming carbide is obviously from one or more walls of the electrolytic cell, it is obvious that the alternative source can come from the oxidation of the anode (for iron-containing anode) component, as a direct additive of the electrolyte medium or from the component of the cathode (for iron-containing cathode), or their arbitrary combination.

[0095] Figure 5 shows the EDS data of sample A, which is consistent with the XRD results of sample A. The EDS data shows the elemental analysis of three locations on the carbon nanomaterial product: Figure 5A The first point is shown to contain 94.9% carbon and 5.1% iron (see Figure 5A In the illustration of + 3 , scale bar: 10 μm), Figure 5B A second location containing 92.4% carbon, 5.8% iron and 1.9% Cr is shown (see Figure 5B +2 position in the inset, scale bar 10 μm); and Figure 5C EDS data obtained at the third position of 100.0 atomic percent carbon is shown.

[0096] Without being bound by any particular theory, the source of the iron that forms the carbides is likely to come from one or more walls of the electrolytic cell. However, alternative sources of iron can come from oxidation of anode (for iron-containing anodes), as direct iron-based additives that can be added to the electrolyte medium, such as cast iron powder, iron metal, steel, stainless steel, or other iron-containing metal alloys, or iron oxides, including (but not limited to) FeO, Fe2O3, Fe3O4, or any other iron-containing salt, etc., or from cathode (for iron-containing cathodes) components, or any combination thereof.

[0097] Figure 6 and Figure 7 Figure 2 is a high-resolution TEM EDS (including bright field (BF), dark field (DF) and high-angle annular dark field (HAADF)) image of two different regions of the synthesized mCNM product. Figure 6 The second region (as shown) is located in the hollow core of the carbon nanotube, and the CNT product has a carbon wall and no metal in the core. Figure 7 ) is the metallic core of the carbon nanotube, and primarily iron and a small amount of nickel are evident.

[0098] Example 5

[0099] As part of the carbon nanomaterial product prepared according to embodiments of the present disclosure, other magnetic CNTs were prepared. In this example, the magnetic CNTs were made with excess iron.

[0100] The electrolysis reaction was carried out using one or more electrolytic cells whose walls comprised stainless steel 304. The electrolyte medium was molten Li2CO3. The electrolytic cell was open to air containing CO2. The anode was made of Incoloy composite (composed of about 40% iron, about 30-35% nickel and about 19-23% chromium), and the cathode was made of Monts brass. The electrolyte was heated to about 0.1A / cm 2The electrolysis reaction takes place at a substantially constant current density and a current of 8 A is applied.

[0101] After about 4 hours of electrolysis, the cathode was removed from the electrolytic cell and cooled. The solid carbon nanomaterial product was stripped from the cathode and washed to remove excess electrolyte medium prior to microscopy.

[0102] Note that with high iron content, the anode can continuously release iron oxide during the electrolysis reaction, and since the electrolysis reaction is at 0.1 A / cm 2 In pure Li2CO3, a decrease in the measured Coulombic efficiency to about 89% is therefore observed.

[0103] Fig. 8A , Figure 8B and Figure 8C Shown are SEM images of the carbon nanomaterial product from this Example 5. The scale bars in these images are 30 μm, 20 μm, and 10 μm, respectively. Fig.8D , Fig. 8E and Figure 8F TEM images of the carbon nanomaterial product from this Example 5 are shown. The scale bars in these images are 500nm, 50nm, and 10nm, respectively. The carbon nanomaterial product contains at least some magnetic CNTs, as shown in FIG8 . Unlike the CNTs shown in FIGS. 2 and 3 , the CNTs shown in FIG8 contain graphene-coated nodules observed outside the CNTs, and the interior of the CNTs is partially filled with sediments. Similarly, nodules and fillings were observed in CNT growth driven by iron carbide using chemical vapor deposition (CVD). In these CVD-formed CNTs, the interior of the nodules and the CNT filling were previously identified as iron carbide. As Figure 8F As shown in the TEM image of Figure 1, the interlayer lattice distance is only 0.20 nm, which is significantly smaller than the 0.33 to 0.34 nm graphene lattice interlayer between CNT graphene walls. Figure 2D Similar to the segregations previously identified in carbon nanostructures and in those previous structures, a distinct 0.20 nm intercrystalline segregation occurred in the carbon nanomaterial product of Example 6, identifying the intercrystalline segregation as iron carbide.

[0104] Example 6

[0105] Based on the previously described embodiments, it is observed that the electrolysis reaction carried out in a Li2CO3 molten electrolyte medium with a low concentration of added Li2O or in an electrolyte medium aged for 24 hours can result in a higher yield of uniform CNTs in the carbon nanomaterial product than the same pure Li2CO3 electrolyte medium that has not been aged. This results in the electrolysis reaction carried out in a cast iron container, rather than a stainless steel container, through an unaged pure molten Li2CO3 electrolyte medium, which can promote the formation of iron carbide of graphite structure and result in a more uniform carbon nanomaterial product of the electrolysis reaction.

[0106] A cast iron container (iron containing 2 to 4.3% carbon, see Fig.9A (i)) was used to carry out the electrolysis reaction of Example 6. The electrolyte medium was Li2CO3 which was heated overnight inside a cast iron container to remove the surface layer of the container. Then, about 300 g of fresh Li2CO3 was added to the container and heated to about 770°C to act as a molten electrolyte medium. The electrolytic cell was open to air containing CO2. The anode was made of Nichrome and the cathode was made of Monts brass. The electrolyte medium was heated to about 0.1 A / cm 2 The electrolysis reaction takes place at a substantially constant current density and a current of 2A is applied.

[0107] After about 4 hours of electrolysis, the cathode was removed from the electrolytic cell and cooled (see Fig.9A (ii) and (iii)). Prior to microscopy, the solid carbon nanomaterial product was stripped from the cathode and washed to remove excess electrolyte medium.

[0108] FIG. 9B to FIG. 9F The SEM image of the carbon nanomaterial product of this Example 6 is shown. Fig. 9B With a scale bar of 200 μm, Fig. 9C With a scale bar of 20 μm, Fig.9D Scale bar with 5 μm, Fig.9E and Fig.9F The scale bar is 10 μm respectively. The magnetic CNTs within the carbon nanomaterial product are highly uniform and have a high aspect ratio (length to diameter). The Coulombic efficiency reaches 100% and the product is uniform (~98% pure) ultrathin, magnetic carbon-nanotubes as measured by EQN.6.

[0109] Without being bound by any particular theory, the embodiments described herein provide ferromagnetic carbon nanotubes as a product of CO2 bubbling through a molten electrolyte medium during an electrolysis reaction or by exposure to air containing CO2 or other CO2 sources. The mechanism of preparation of mCNTs appears to be through a magnetic material addition process or a carbide nucleation process, rather than a transition metal mediated process. It was also observed in Example 6 that the use of a cast iron container as an electrolytic cell for CO2 electrolysis using a molten lithium carbonate electrolyte medium produced uniform mCNTs with a high aspect ratio in an efficient Coulombic manner.

Claims

1. A method for producing a magnetic carbon nanomaterial product, the method comprising: (a) heating the electrolyte medium to obtain a molten electrolyte medium; (b) positioning the molten electrolyte medium between an anode and a cathode of an electrolytic cell; (c) introducing a magnetic additive component into the electrolytic cell; (d) introducing a carbon source into the electrolytic cell; (e) applying an electric current to the cathode and the anode in the electrolytic cell; as well as (f) collecting the magnetic carbon nanomaterial product from the cathode, wherein the magnetic carbon nanomaterial product is movable with a magnetic field, the magnetic carbon nanomaterial product comprises a plurality of individual constituent magnetic nanostructures, and wherein a magnetic additive component is introduced outside the base of each individual constituent magnetic nanostructure within the magnetic carbon nanomaterial product.

2. The method according to claim 1, wherein: The magnetic additive component is present in each individual composition structure in an amount greater than 1 wt %.

3. The method according to claim 1, wherein: The magnetic additive component is introduced into each individual composition structure.

4. The method according to claim 1, wherein: The magnetic additive component includes a magnetic material addition component, a carbide growth component or any combination thereof.

5. The method according to claim 1 also includes selecting the nanomorphology of the magnetic nanostructure that constitutes the magnetic carbon nanomaterial product to include a magnetic carbon nanotube product, a magnetic carbon nanofiber product, a magnetic carbon sheet product, a magnetic graphene product, a magnetic carbon nanoonion product, a magnetic hollow carbon nanosphere product or any combination thereof.

6. The method according to claim 1, wherein: The magnetic additive component includes at least one of the following: a magnetic material addition component, a carbide growth component, or any combination thereof.

7. The method according to claim 6, wherein: The magnetic material additive component is one or more of the following: iron, nickel, cobalt, gadolinium, samarium, neodymium, steel, and alloys including one or more magnetic materials having ferromagnetic properties, paramagnetism, diamagnetic properties or any combination thereof.

8. The method according to claim 6, wherein: The carbide growth component is a metal carbide.

9. The method according to claim 8, wherein: The metal carbide is one of the following: iron carbide, nickel carbide, cobalt carbide, zirconium carbide, chromium carbide, tantalum carbide, hafnium carbide or any combination thereof.

10. The method according to claim 6, wherein: The carbide growth component is a non-metallic carbide.

11. The method according to claim 10, wherein: The non-metal carbide is one of the following: silicon carbide, germanium carbide or any combination thereof.

12. The method according to claim 1, wherein: The magnetic additive component originates from one or more walls of the electrolytic cell, the anode, the cathode, the electrolyte medium, or any combination thereof.

13. A system for producing a magnetic carbon nanomaterial product, the system comprising: (a) an electrolytic cell comprising one or more walls defining a plenum chamber; (b) electrolyte medium; (c) a carbon source; (d) an anode and a cathode positioned within the plenum chamber, wherein the plenum chamber is configured to receive the electrolyte medium and carbon from the carbon source therein; (e) a magnetic additive component for implementing a magnetic additive process, a carbon driven process, or a combination thereof, and (f) a collection magnet for attracting the carbon nanomaterial product from the cathode of the electrolytic cell, The electrolytic cell is further configured to generate or receive an electric current that can be applied to the anode and the cathode to induce an electrolytic reaction for preparing the magnetic carbon nanomaterial product, wherein the magnetic carbon nanomaterial product can be moved by a magnetic field.

14. The system according to claim 13, wherein: The magnetic additive component originates from one or more walls of the electrolytic cell, the anode, the cathode, the electrolyte medium, or any combination thereof.

15. The system of claim 13, further comprising a heater for at least one of: for melting the electrolyte medium and for maintaining the electrolyte medium in a molten state.

16. The system of claim 13, wherein: The anode is made of a material including nickel, iron, chromium or any combination thereof.

17. The system of claim 13, wherein: The metal carbide is iron carbide, nickel carbide, cobalt carbide, zirconium carbide, chromium carbide, tantalum carbide, hafnium carbide or any combination thereof.

18. The system of claim 13, wherein: The non-metal carbide is silicon carbide, germanium carbide or any combination thereof.

19. The system of claim 13, wherein: The carbon source is atmospheric carbon dioxide, an electrolyte medium, or any combination thereof.

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