US20100035775A1 - Microwave-assisted synthesis of carbon and carbon-metal composites from lignin, tannin and asphalt derivatives and applications of same - Google Patents

Microwave-assisted synthesis of carbon and carbon-metal composites from lignin, tannin and asphalt derivatives and applications of same Download PDF

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US20100035775A1
US20100035775A1 US12/487,323 US48732309A US2010035775A1 US 20100035775 A1 US20100035775 A1 US 20100035775A1 US 48732309 A US48732309 A US 48732309A US 2010035775 A1 US2010035775 A1 US 2010035775A1
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carbon
metal
nanocomposites
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Tito Viswanathan
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University of Arkansas
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University of Arkansas
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Assigned to BOARD OF TRUSTEES OF THE UNIVERSITY OF ARKANSAS reassignment BOARD OF TRUSTEES OF THE UNIVERSITY OF ARKANSAS ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: VISWANATHAN, TITO
Publication of US20100035775A1 publication Critical patent/US20100035775A1/en
Priority to US12/751,185 priority patent/US8647512B2/en
Priority to PCT/US2010/029454 priority patent/WO2011008315A1/en
Priority to US12/754,336 priority patent/US8920688B2/en
Priority to PCT/US2010/029978 priority patent/WO2010115199A1/en
Priority to US13/069,132 priority patent/US8753603B2/en
Priority to US13/069,057 priority patent/US20110171108A1/en
Priority to US13/069,097 priority patent/US8790615B2/en
Priority to US13/335,418 priority patent/US8574337B2/en
Priority to US13/767,076 priority patent/US9643165B2/en
Priority to US13/843,106 priority patent/US9095837B2/en
Priority to US14/134,992 priority patent/US9169139B2/en
Priority to US15/474,281 priority patent/US10293329B2/en
Priority to US16/380,174 priority patent/US10974230B2/en
Priority to US17/152,922 priority patent/US12005429B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1026—Alloys containing non-metals starting from a solution or a suspension of (a) compound(s) of at least one of the alloy constituents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/08—Other phosphides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/788—Of specified organic or carbon-based composition

Definitions

  • superscript “13” represents the 13th reference cited in the reference list, namely, Liu, Shuling; Liu, Xinzheng; Xu, Liqiang; Qian, Yitai; Ma, Xicheng, Controlled synthesis and characterization of nickel phosphide nanocrystal, Journal of Crystal Growth (2007), 304(2), 430-434.
  • the present invention relates generally to a method or process of synthesizing carbon and carbon-metal composites, and more particularly to a microwave-assisted method or process of synthesizing carbon and carbon-metal composites from carbon-containing precursors, such as lignins, tannins, lignosulfonates, tanninsulfonates, and their derivatives, and applications of same.
  • carbon-containing precursors such as lignins, tannins, lignosulfonates, tanninsulfonates, and their derivatives, and applications of same.
  • Plants represent an enormous source of biomass, predominantly consisting of lignin and cellulose, and rank on top in terms of the volume of renewable resource materials found in nature.
  • Wood comprises of about 20% lignin, and is separated from cellulose by different methods including sulfite pulping, Kraft and organosolv method.
  • the cellulose produced is mainly used in paper manufacturing but leaves behind an enormous quantity of lignin by-product. It is estimated that less than 2% of the lignin produced in the world is used. 1
  • the main uses for lignin are in the area of dispersants, adhesives and surfactants.
  • Lignin has a complex structure that superficially resembles phenol-formaldehyde resin.
  • lignin monomeric units namely, guaiacyl (significant in soft wood), syringyl and sinepyl alcohol all of which contain a phenylpropenoid unit in their structure.
  • FIG. 1 shows the structure of the three different types of alcohols/phenols, namely, (a) guaiacyl, (b) syringyl and (c) sinapyl alcohol in lignin, respectively.
  • FIG. 1 The structures shown in FIG. 1 indicate that lignin is a significant source of aromatics and could in theory and in practice compete with petroleum as an aromatic hydrocarbon resource. Extensive research on lignin utilization has been carried out over several decades but has taken on even more importance with the prospect of dwindling petroleum resources.
  • carbon fiber feedstocks are derived from polyacrylonitrile, pitch and rayon.
  • lower costs are required for penetration in high volume applications such as their use as carbon composites in high strength and light weight transport vehicles.
  • Carbon fibers may be made by treating lignin fibers at 1000° to 2000° C. while maintaining a fibrous structure during a stabilization stage in which the fibers are heated under tension at 200°-300° C. in presence of air.
  • Low cost carbon fibers from lignin have been shown to be feasible by researchers at Oakridge National Laboratory, Oak Ridge, Tenn. 2
  • Activated carbon fibers and metal composites have been prepared from lignin by an acid treatment and fiber formation using extrusion or melt spinning techniques, followed by progressive heating to 400° C. ( ⁇ 500° C.).
  • 3 In a related research flash carbonization of biomass by controlled ignition at elevated pressures within a packed bed has been achieved by researchers at the Hawaii Natural Energy Institute.
  • 4 Multi-walled carbon nanotubes (MWCNTs) have been obtained from grass by heating in presence of oxygen. Rapid heat treatment at ⁇ 600° C. in presence of oxygen converts the vascular bundles into CNTs. The procedure is tedious considering numerous heating and cooling cycles have to be performed for CNT formation.
  • Nanocarbons with controlled morphology have been prepared by microwave heating of conducting polymers. It was found that doped-polypyrrole, -polythiophene and -poly(ethylenedioxythiophene) (PEDOT) can be carbonized by simple microwave heating. 6
  • Carbon-metal nanocomposites represent a new class of materials with niche applications in a variety of areas including electromagnetic interference (EMI) and radar shielding, fuel cells, capacitors, catalysts and solar cells.
  • Nickel nanotubes encapsulated in CNTs have been obtained via the pyrolysis of ethylene on an array of nickel nanotubes. The procedure calls for the use of ethylene gas at 650° C. heated by conventional means.
  • 7 Synthesis of carbon-supported Pt nanoparticles for fuel cell application have been accomplished by microwave treatment of H 2 PtCl 6 in presence of carbon black. 8 Cu-doped carbon composites may be used as electrode materials for electrochemical capacitors.
  • the composite was prepared by combining a phenolic resin, ferrocene, hexamethylenetetramine, and Cu(CH 3 COO) 2 2H 2 O and heated at 800° C. in nitrogen atmosphere and activated in steam at 800° C. for different time periods.
  • Nickel phosphide Ni 2 P on silica support has been shown to exhibit excellent performance characteristics in both hydrodenitrogenation (HDN) as well as hydrodesulfurization (HDS) with activities greater than commercially available mixed transition metal Ni—Mo—S/Al 2 O 3 catalyst. 11
  • Ni 2 P as an outstanding catalyst for both HDN and HDS has attracted interest in the synthesis of nickel phosphides. 12
  • Prior techniques have included the combination of the elements under extreme temperature and pressure, reaction of metal chloride with phosphine gas, decomposition of complex organometallics, electrolysis and reduction of phosphate with gaseous hydrogen. 10 These techniques are neither economically attractive nor quick or safe, for large scale commercial manufacture in an industrial setting.
  • Ni 2 P nanocrystals A method for controlled synthesis of Ni 2 P nanocrystals has been reported recently by Liu et al. 13
  • the procedure involves reacting yellow phosphorous and Ni 2 SO 4 in ethylene glycol:water solvent in an autoclave at 180° C. for 12 hours.
  • the black solid product is filtered and washed with absolute ethanol, benzene and water.
  • the XRD of the product showed that it was Ni 2 P and the morphology was dendritic as determined by SEM.
  • the mechanism of the formation of the product was thought to involve the formation of PH 3 upon the reaction of P with water and with H 3 PO 4 . Once generated nickel ions were theorized to combine with PH 3 to form Ni 2 P.
  • Xie et. al 14 have reported the synthesis of irregular Nickel phosphide nanocrystals containing Ni, Ni 3 P, Ni 5 P 2 and Ni 12 P 5 by a milder route using NiCl 2 and sodium hypophosphite as reactants at 190° C. The product after reflux was washed with ammonia and ethanol. Copper phosphide hollow spheres have been synthesized in ethylene glycol by a solvothermal process using copper hydroxide and elemental phosphorus as starting material using an autoclave at 200° C. for 15 hours. 15
  • the present invention in one aspect, relates to a plurality of carbon-metal nanocomposites.
  • the plurality of carbon-metal nanocomposites includes a plurality of carbons with a molecular structure that shows a first peak in the range of 1585 to 1565 cm ⁇ 1 in a corresponding Raman spectrum, and a second peak in the range of 1325 to 1355 cm ⁇ 1 in the corresponding Raman spectrum, wherein the first peak represents carbons with a graphitic nature and the second peak represents nanodiamonds, and wherein the plurality of carbon-metal nanocomposites is made from a metal derivative or metal chelated derivative of a carbon-containing precursor in solid form that is subjected to microwave radiation at a frequency in the range of 900 MHz to 5.8 GHz, for a period of time effective to allow the plurality of carbon-metal nanocomposites to be formed.
  • the metal of the metal derivative or metal chelated derivative is selected from the group consisting of Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au and a combination thereof.
  • the carbon-containing precursor is selected from the group consisting of lignin, lignosulfonate, tannin, tanninsulfonate and sulfonated asphalt.
  • the metal of the metal salt is selected from the group consisting of Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au and a combination thereof.
  • the carbon-containing precursor is selected from the group consisting of ammonium lignosulfonate, ammonium tanninsulfonate and ammonium asphaltsulfonate.
  • the microwave absorber is selected from the group consisting of metal particles, phosphoric acid, hydrated NaH 2 PO 4 , CO 2 O 3 , CuO, MnO 2 , NiO, Fe 3 O 4 , WO 3 , Ag 2 O, Au 2 O 3 , non-stoichiometric oxides of titanium (TiO 2-x ) and a carbon allotrope, wherein the carbon allotrope is selected from the group consisting of carbon black, fullerene, graphite and carbon nanotubes.
  • the carbon-containing precursor further comprises a dispersion of a metal salt, wherein the metal of the metal salt is selected from the group consisting of Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au and a combination thereof.
  • the metal of the metal salt is selected from the group consisting of Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au and a combination thereof.
  • the present invention in a further aspect, relates to a plurality of carbon-metal nanocomposites.
  • the plurality of carbon-metal nanocomposites includes a plurality of carbons with a molecular structure that shows a first peak in the range of 1585 to 1565 cm ⁇ 1 in a corresponding Raman spectrum, and a second peak in the range of 1325 to 1355 cm ⁇ 1 in the corresponding Raman spectrum, wherein the first peak represents carbons with a graphitic nature and the second peak represents nanodiamonds, and wherein the plurality of carbon-metal nanocomposites is made from a sample of metal ions and an organic compound that is subjected to microwave radiation at a frequency in the range of 900 MHz to 5.8 GHz, for a period of time effective to allow the plurality of carbon-metal nanocomposites to be formed.
  • the present invention in yet another aspect, relates to an article of manufacture.
  • the article of manufacture includes a plurality of carbon-metal nanocomposites that has a plurality of carbons with a molecular structure that shows a first peak in the range of 1585 to 1565 cm ⁇ 1 in a corresponding Raman spectrum, and a second peak in the range of 1325 to 1355 cm ⁇ 1 in the corresponding Raman spectrum, wherein the first peak represents carbons with a graphitic nature and the second peak represents nanodiamonds, respectively.
  • FIG. 1 shows structures of (a) guaiacyl, (b) syringyl and (c) sinapyl alcohol in lignin.
  • FIG. 2 shows an XRD spectrum of Ni 2 P generated according to one embodiment of the present invention.
  • FIG. 3 shows an image of an SEM of Ni 2 P synthesized according to one embodiment of the present invention, (a)-(c) at different amplification rates.
  • FIG. 4 shows an XRD spectrum of Ni 2 P/C made in presence of silica according to one embodiment of the present invention.
  • FIG. 6 shows the molecular structure of a dimeric unit of tannin complexed to a metal ion.
  • FIG. 7 shows an XRD spectrum of Ni—C composite prepared by the novel method.
  • FIG. 8 shows that the temperature increases when 1 g lignin is microwaved with 50 mg graphite powder and 50 mg carbon black powder in a 950 W microwave operating at 2.45 GHz.
  • FIG. 9 shows an XRD spectrum with distinctive peaks of carbon obtained from microwaving tannin according to one embodiment of the present invention.
  • FIG. 10 shows an XRD spectrum with distinctive peaks of carbon obtained from microwaving lignin according to one embodiment of the present invention.
  • FIG. 11 shows an XRD spectrum for a carbon-nickel composite synthesized by microwaving a tannin-nickel complex according to one embodiment of the present invention.
  • FIG. 12 shows a Raman spectrum of carbon produced from microwaving tannin (without added carbon) according to one embodiment of the present invention. The wavelength is followed by the intensity of the signal.
  • FIG. 13 shows a Raman spectrum of carbon produced from microwaving tannin (without added carbon) according to one embodiment of the present invention. The wavelength is followed by the intensity of the signal.
  • FIG. 14 shows a Raman spectrum of lignin produced by microwaving lignin (without added carbon) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • FIG. 15 shows a Raman spectrum of lignin produced by microwaving lignin (without added carbon) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • FIG. 16 shows a Raman spectrum of carbon produced from tannin-formaldehyde condensation product (no carbon added) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • FIG. 17 shows a Raman spectrum of carbon produced from tannin-formaldehyde condensation product (no carbon added) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • FIG. 18 shows a Raman spectrum of carbon composite prepared by microwaving nickel-tannin composite (no carbon added) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • FIG. 19 shows a Raman spectrum of carbon composite prepared by microwaving nickel-tannin composite (no carbon added) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • FIG. 20 shows a Raman spectrum of carbon composite prepared by microwaving iron (III)-lignosulfonate (no carbon added) according to one embodiment of the present invention. Number following frequency of signal (if shown) represents intensity.
  • FIG. 21 shows a Raman spectrum of carbon composite prepared by microwaving iron (III)-lignosulfonate (no carbon added) according to one embodiment of the present invention. Number following frequency of signal (if shown) represents intensity.
  • FIG. 22 shows a flow diagram illustrating a synthesis process of making Ni—C composite according to one embodiment of the present invention.
  • “around”, “about” or “approximately” shall generally mean within 20 percent, preferably within 10 percent, and more preferably within 5 percent of a given value or range. Numerical quantities given herein are approximate, meaning that the term “around”, “about” or “approximately” can be inferred if not expressly stated.
  • SEM scanning electron microscope
  • X-ray diffraction refers to one of X-ray scattering techniques that are a family of non-destructive analytical techniques which reveal information about the crystallographic structure, chemical composition, and physical properties of materials and thin films. These techniques are based on observing the scattered intensity of an X-ray beam hitting a sample as a function of incident and scattered angle, polarization, and wavelength or energy. In particular, X-ray diffraction finds the geometry or shape of a molecule, compound, or material using X-rays. X-ray diffraction techniques are based on the elastic scattering of X-rays from structures that have long range order. The most comprehensive description of scattering from crystals is given by the dynamical theory of diffraction.
  • nanoscopic-scale As used herein, “nanoscopic-scale,” “nanoscopic,” “nanometer-scale,” “nanoscale,” the “nano-” prefix, and the like generally refers to elements or articles having widths or diameters of less than about 1 ⁇ m, preferably less than about 100 nm in some cases.
  • specified widths can be smallest width (i.e. a width as specified where, at that location, the article can have a larger width in a different dimension), or largest width (i.e. where, at that location, the article's width is no wider than as specified, but can have a length that is greater).
  • the present invention in one aspect, relates to a novel method or process for the conversion of biomass renewable resources materials into carbon and carbon-metal nanostructures.
  • the method is an environmentally friendly process that may revolutionize carbon black and related industries by making use of massive quantities of by-products from the forest product industries and steer away from non-renewable resources such as natural gas, petroleum, and coal for the generation of carbon materials.
  • the process also allows the synthesis of carbon-metal nanocomposites, where the metal is either in the elemental state or is a tetralide, pnictide or chalcogenide, for example a carbide, nitride or an oxide.
  • the materials synthesized according to various embodiments of the present invention represent technologically diverse multifunctional materials by an extremely inexpensive and environmentally friendly process.
  • the novel nanometal derivatives synthesized according to various embodiments of the present invention represent an entirely new line of nanocomposites with unique morphologies with potential applications in a variety of fields some of which may be hitherto unknown.
  • Ni 2 P Nickel phosphide synthesized according to various embodiments of the present invention, one is its use as a catalyst for the removal of sulfur and nitrogen from petroleum feedstocks—a problem of extreme urgency because of the prediction of decreased Arab oil resources and increased reliance on Canadian tar sands with increased Sulfur and Nitrogen content.
  • the process according to various embodiments of the present invention is quick and inexpensive in comparison to the known technologies. Moreover, it represents a deviation from conventional heating source as well as raw materials, many of which are non-renewable resource based. It also allows the formation of metal nanoparticles either pristine or on carbon support with high surface area. Additionally, the process simultaneously reduces metal ions during the process of carbonization and produces nanoparticles of both carbon and metal.
  • the metal obtained may be a zero valent metal or one of the metal tertralides, pnictides, chalcogenides, borides or carbides depending on the reactants present during the synthetic process.
  • the process also allows the formation of unique carbon nanostructures including nanodiamonds.
  • the present invention in another aspect, relates to a novel method or process for synthesizing carbon-metal composites using metal ions in presence of an organic compound, which is one of cellulose; hydroxyalkylcellulose such as hydroxyethylcellulose, methylcellulose, carboxymethylcellulose; cyclodextrins; chitin and chitosan; starch; guar gum and polysaccharides.
  • an organic compound which is one of cellulose; hydroxyalkylcellulose such as hydroxyethylcellulose, methylcellulose, carboxymethylcellulose; cyclodextrins; chitin and chitosan; starch; guar gum and polysaccharides.
  • the present invention in yet another aspect, relates to a novel method or process for synthesizing metal particles in the reducing or non-oxidizing environment generated during the microwave process without the need to use reducing gases, such as H 2 gas, or inert gases, such as Ar and N 2 gases, during the process, where the process in one embodiment allows simultaneously producing carbon from lignin and reducing the metal ions, such as Ni, Cu, to elemental metal such that nanoparticles of carbon and metal are produced after dispersion.
  • reducing gases such as H 2 gas, or inert gases, such as Ar and N 2 gases
  • the present invention in a further aspect, relates to a novel method or process for synthesizing Ni 2 P nanoparticles in the reducing or non-oxidizing environment generated during the microwave process without the need to use reducing gases, such as H 2 gas, during the process.
  • reducing gases such as H 2 gas
  • the present invention in another aspect, relates to a novel method or process for synthesizing Cu 3 P and Cu 2 S nanoparticles in the reducing or non-oxidizing environment generated during the microwave process without the need to use reducing gases, such as H 2 gas, during the process.
  • reducing gases such as H 2 gas
  • the present invention in yet another aspect, relates to a process for the preparation of carbon nanostructures as well as carbon-metal nanostructures by applying microwave radiation to a carbon-containing precursor, such as lignins, tannins, lignosulfonates, tanninsulfonates and their derivatives.
  • a carbon-containing precursor such as lignins, tannins, lignosulfonates, tanninsulfonates and their derivatives.
  • the microwave radiation is applied at a frequency of 900 MHz to 5.8 GHz, or more preferably at a frequency of 2.45 GHz for a period of 30 seconds to 60 minutes, or more preferably for a period between 4 minutes and 30 minutes.
  • the process may take place either in the presence of air, in the presence of a non-oxygenated atmosphere or in the absence of air.
  • the precursor is a metal derivative or a metal chelated derivative of a carbon-containing material and the end result is a carbon-metal composite.
  • the metal may be Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au or a mixture of any of the preceding.
  • the carbon-containing precursor may be lignin, lignosulfonate, tannin, tanninsulfonate or sulfonated asphalt.
  • the metal derivative or metal chelated derivative may have undergone alkali treatment to convert the metal to a metal oxide.
  • the metal is preferably Co, Cu, Mn, Ni, Fe or W.
  • the process may be assisted by the presence of a microwave absorber.
  • the microwave absorber may include metal particles, phosphoric acid, hydrated NaH 2 PO 4 , CO 2 O 3 , CuO, MnO 2 , NiO, Fe 3 O 4 , WO 3 , Ag 2 O, Au 2 O 3 , a non-stoichiometric oxide of titanium (TiO 2-X ) or a carbon allotrope, such as carbon black, fullerene, graphite and carbon nanotubes.
  • the precursor is an ammonium salt of a carbon-containing material and the process is carried out in the presence of a metal salt, either with or without the presence of a microwave absorber.
  • the metal of the metal salt may include Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au or and mixtures of any of the preceding.
  • the metal salt may be an oxalate, an acetate, a sulfate or a chloride.
  • the precursor may be ammonium lignosulfonate, ammonium tanninsulfonate and ammonium asphaltsulfonate.
  • the microwave absorber may include metal particles, phosphoric acid, hydrated NaH 2 PO 4 , CO 2 O 3 , CuO, MnO 2 , NiO, Fe 3 O 4 , WO 3 , Ag 2 O, Au 2 O 3 , a non-stoichiometric oxide of titanium (TiO 2-x ) or a carbon allotrope, such as carbon black, fullerene, graphite and carbon nanotubes.
  • the precursor is a carbon-containing material dispersed with a metal salt.
  • the metal salt may have undergone alkali treatment. In either alternative, the process may be assisted by the presence of a microwave absorber.
  • the metal of the metal salt may be Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au or a mixture of any of the preceding.
  • the precursor may be sucrose, lactose, starch, polysaccharide, phenol-formaldehyde resin, naphthalenesulfonic acid-formaldehyde copolymer, polyvinyl alcohol, asphaltsulfonate, lignin, lignosulfonate, tannin or tanninsulfonate.
  • the microwave absorber may include metal particles, phosphoric acid, hydrated NaH 2 PO 4 , CO 2 O 3 , CuO, MnO 2 , NiO, Fe 3 O 4 , WO 3 , Ag 2 O, Au 2 O 3 , a non-stoichiometric oxide of titanium (TiO 2-x ) or a carbon allotrope, such as carbon black, fullerene, graphite and carbon nanotubes.
  • the process may be used for making carbon particles by starting with a carbon-containing precursor, with or without a microwave absorber.
  • the precursor may include lignin, tannin, asphalt and their derivatives.
  • the precursor may also include an ammonium derivative of lignin, an alkali metal lignosulfonate, tanninsulfonate, sulfonated asphalt, wood, sawdust, sucrose, lactose, cellulose, starch, polysaccharide, organic garbage, pitch derived from petroleum or coal or a carbon-containing polymer, such as polybenzimidazole, polybutadiene, polyethylene, polyvinyl alcohol, polyimides, polystyrene, rayon, polypropylene, nylon, phenol-formaldehyde resin or naphthalenesulfonic acid-formaldehyde copolymer.
  • the microwave absorber may include metal particles, phosphoric acid, hydrated NaH 2 PO 4 , CO 2 O 3 , CuO, MnO 2 , NiO, Fe 3 O 4 , WO 3 , Ag 2 O, Au 2 O 3 , a non-stoichiometric oxide of titanium (TiO 2-x ) or a carbon allotrope, such as carbon black, fullerene, graphite and carbon nanotubes.
  • a one gram sample of the wood byproduct is dissolved in water, 0.25 g of powdered graphite is added and mixed thoroughly using a sonicator. The water is evaporated and the dry powder is then placed inside a microwave oven under a hood. The oven is then turned on for a duration of 4 minutes. The sample sparks momentarily and glows red during the entire process. The sample may then be optionally heated further or the reaction may be terminated. The black sample is then powdered using a mortar and pestle and then introduced in a Erlenmeyer flask.
  • DI deionized
  • the lignosulfonate salt is converted to the desired metal lignosulfonate salt prior to carbonization.
  • a 10 g sample of calcium lignosulfonate, which has 5% Ca 2+ (0.0125 mol Ca ions) is added to 70 mL of DI water and heated to 90 degrees C. with stirring.
  • a 0.0125 mol sample of metal sulfate (copper, cobalt, nickel, iron, zinc, etc.) is then added to the solution and the reaction mixture heated for one hour at 90 degrees C.
  • the solution is then cooled and filtered through a coarse filter paper to remove the CaSO 4 and the filtrate is then heated at 85 degrees C. until the water evaporates.
  • a 1 g sample is treated with 4 drops of 85% phosphoric acid and thoroughly mixed using a mortar and pestle. It is then subjected to microwave radiation using a 950 watt microwave oven placed under a hood for 2 minutes. It is then subjected to further 4 minutes of microwave treatment. The sample is cooled and introduced into a mortar and pestle and powdered. The sample is treated in boiling water for 10 minutes and cooled and filtered through suction. It is then washed with 4 ⁇ 100 mL of DI water and dried on the filter paper under suction. It is further dried in a vacuum oven in room temperature overnight.
  • alkali is added to convert the metal lignosulfonate or a metal chelated derivative to a metal oxide which becomes an excellent microwave absorber.
  • the heat generated is sufficient to carbonize the lignin and to make metal in the zero valence state by reaction with carbon.
  • Lignin, tannin and asphalt and their derivatives are preferred, although not the sole or reuired, materials for use in the practice of the present invention. These materials are widely available and may occur as byproducts or wastes from other industrial operations.
  • Lignin the major non-cellulosic constituent of wood, is a complex phenolic polymer that bears a superficial resemblance to phenol-formaldehyde resins. It consists of functionalized phenylpropane units connected via alkyl and aryl ether linkages. Essentially, all of the lignin commercially available is isolated as by-products from the paper industry from either the sulfite or the Kraft process.
  • Sulfonated lignins are obtained either as spent sulfite liquor (SSL) or by sulfonation of lignin obtained from the Kraft process.
  • SSL obtained from the sulfite process consists of lignosulfonates (approximately 55%), sugars (30%), and other ingredients in smaller amounts.
  • a typical monomeric unit of Kraft lignin that has been sulfomethylated at the aromatic ring and sulfonated on the aliphatic side chain has the following chemical structure:
  • Sulfomethylation is accomplished by the reaction of the Kraft lignin with formaldehyde and sodium sulfite.
  • the aliphatic sulfonation occurs preferentially at the benzylic position of the side chain of the phenylpropane units.
  • Lignosulfonates are available are available as sodium salts (Reax® 825E, Kraftsperse® and Polyfon® from MeadWestvaco, for example) and are cheaper alternatives to other forms of lignosulfonates.
  • LignoTech's calcium salt of lignosulfonic acid (Borresperse CA) is especially suitable for the synthesis of metal-carbon nanocomposites.
  • Metal lignosulfonates and metal chelated lignosulfonates are readily available from a variety of manufacturers. For example, iron lignosulfonate and ferrochrome lignosulfonate are extensively used in the petroleum industry. Also metal chelated lignosulfonate where the metal ion is either magnesium, copper, zinc, iron or manganese is used in the agricultural industry. These products are used as inorganic micronutrients along with fertilizers during farming. Examples of metal chelated lignosulfonates are Borrechel FE, Borrechel MN, Borrechel CU and Borrechel ZN available from LignoTech.
  • MeadWestvaco and LignoTech USA are two of the major manufacturers of lignosulfonates in the U.S. and a variety of sulfonated lignin products are available from them.
  • the sulfonation can be controlled to occur either at the aromatic ring or the benzylic position or both.
  • the degree and position of sulfonation can affect the final property and potential application of the lignin.
  • Tannins are naturally occurring polyphenols that are found in the vascular tissue of plants such as the leaves, bark, grasses, and flowers. They are classified into two groups: condensed tannins and hydrolysable tannins. The reaction scheme for the sulfonation of monomeric unit of a condensed tannin is illustrated below:
  • the structure consists of three rings: two benzene rings on either side of an oxygen-containing heterocyclic ring.
  • the A-ring to the left of the cyclic ether ring consists of one or two hydroxyl groups.
  • the B-ring present on the right of the cyclic ether ring also consists of two or three hydroxyl groups.
  • a particular tannin of interest is Quebracho tannin.
  • This tannin is obtained from the hot water extraction of the heartwoods of Schinopsis balansae and lorentzii , indigenous to Argentina and Paraguay. Quebracho accounts for 30% of the dry weight of the heartwoods with a production level averaging 177,000 tons per year over the past 30 years, according to the Tannin Corporation, Peabody, Mass.
  • Sulfonated tannins are commercially available and represent an inexpensive renewable resource. For example, Chevron Philips Chemical in The Woodlands, Tex. supplies tannins with different degrees of sulfonation. The MSDSs and technical data sheets providing the structure and percentage of sulfur in the products are also provided. Sold under the trade name of “Orfom®” tannins, these represent an alternate source of a sulfonated renewable resource that could be compared to sulfonated lignins.
  • Sulfonated asphalts are used extensively in the petroleum industry. They are produced by the sulfonation of asphalt which is a derived from petroleum. Suppliers of sulfonated asphalt include Chevron Phillips in the USA and Flowline Solutions in Calgary, Canada.
  • Calcium lignosulfonate was converted to metal lignosulfonate by treatment with metal sulfate followed by filtration to remove CaSO 4 .
  • the metal lignosulfonate was then treated with aqueous NaOH to yield a lignosulfonate-metal oxide nanocomposite, which was then subjected to microwave radiation at 2.45 MHz operating at 950 W, for different time periods.
  • Borresperse CA calcium lignosulfonate
  • the mechanism by which the transformation occurs probably involves the conversion of metal ions into metal oxide by the action of base.
  • the excellent microwave absorption by the metal oxide results in a “thermal runaway” phenomenon resulting in high temperature carbonization of the lignin, eliminating some oxides of carbon during the transformation with concomitant reduction of the metal oxide to metal.
  • the microwave heating of metal oxides generates a heat flow from “inside” of the sample towards to the “outside” of the sample, which results in a more uniformly, efficient, effective and rapid heating pattern.
  • This example illustrates a method or process according to one embodiment of the present invention.
  • an exemplary process for synthesizing Ni—C nanocomposites is schematically shown according to one embodiment of the present invention.
  • a certain amount of lignosulfonate salt is converted to desired metal lignosulfonate salt prior to carbonization.
  • a 10 g sample of calcium lignosulfonate, which has 5% Ca 2+ (0.0125 mol Ca ions) is added to 70 mL of DI water in a container to form a solution.
  • the solution is heated to a temperature range of about 85-90 degrees C. with stirring.
  • a 0.0125 mol sample of nickel sulfate, NiSO 4 is then added to the solution to form a reaction mixture.
  • metal salts with metals such as Sb, Li, Rb, Ti, V, Mn, Fe, Co, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au or any mixture of them, can also be utilized.
  • the reaction mixture is mixed well. And at step 2205 , the reaction mixture is heated for at a temperature at about 90° C. for a period of time effective to allow the following chemical reaction to take place:
  • period of time effective is about one hour, which may be different if other metal salts are used.
  • the resultant solution is then cooled and filtered through a coarse filter paper using vacuum suction to remove the CaSO 4 to result in a filtrate having nickel lignosulfonate in solution, namely NiLSO 3 +H 2 O, at step 2208 .
  • the filtrate is heated at 85 degrees C. until the water evaporates, which results in nickel lignosulfonate (i.e., NiLSO 3 ) in solid form at step 2210 .
  • NiLSO 3 nickel lignosulfonate
  • a 3 mL aliquot of 6M NaOH can be added to the filtrate and the solution was heated with agitation at 90° C. until all the water evaporated.
  • the NiLSO 3 in solid form is then furthered dried in a vacuum oven overnight at room temperature. Typical yield is around 85-90%.
  • the calcium salt sodium salts in presence of metal salts may be used a starting materials for the preparation of carbon-metal nanocomposites in which case the filtration step, step 2207 , is not needed.
  • the dried NiLSO 3 in solid form is powdered.
  • the powdered NiLSO 3 sample is placed in a crucible and subjected to microwave radiation at 2.45 MHz from a tabletop microwave oven operating at 950 W. Depending on the metal, after a visible red glow (approximately 5 minutes) the sample was subjected to an additional microwave exposure for 4 minutes. All experiments were carried out in ambient atmosphere. After termination of the microwave radiation the sample was scraped from the crucible, powdered and washed with excess water. Filtration followed by drying produced a black powder of Carbon Nickel composites in approximately 25% yield (from calcium lignosulfonate).
  • metals here Ni
  • carbons can be removed to produce a collection of only metal (here Ni) nanoparticles.
  • This example describes Ni 2 P nanoparticles that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 3 shows an SEM image of the sample, which shows that the morphology of the sample is in the form of nanospheres, with an average nanosphere size of ⁇ 100 nm.
  • the fold seen in the middle of the image is likely due to a tape that is used to support the sample.
  • Ni 2 P nanoparticles that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it. In this example, however, Ni 2 P nanoparticles are synthesized on a silica support.
  • FIG. 4 shows an XRD of Ni 2 P prepared in the presence of silica. It can be seen that all the peaks expected from Ni 2 P are present in the sample. In addition, the characteristic peaks for carbon and silica are also present, respectively. No other peaks are discernable indicating that SiO 2 remains unaffected under the reaction conditions.
  • This example describes Cu 3 P nanoparticles that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 5 shows an SEM image of cuprous phosphide (Cu 3 P) nanoparticles that are synthesized according to one embodiment of the present invention.
  • the EDX of the region shown on the SEM image is shown on the right. It can be seen from the Table corresponding to the EDX data that there are three copper atoms to every phosphorus atom.
  • the nanoparticles obtained may be described as being comprised of nanospheres decorated with needles.
  • This example describes Tannins that are utilized to practice the present invention.
  • Tannins are naturally occurring polyphenols that are found in the vascular tissue of plants such as the leaves, bark, grasses, and flowers. Tannins are classified into two groups 16 : condensed tannins or proanthocyanidins and hydrolysable tannins from the polyesters of gallic acids.
  • FIG. 6 illustrates the structure of a monomeric unit of condensed tannin with Nickel ion complexed to the catechol structure, which is excellent for chelating metal ions.
  • a particular tannin of interest is Quebracho tannin.
  • This tannin is obtained from the hot water extraction of the heartwoods of Schinopsis balansae and lorentzii , indigenous to Argentina and Paraguay. Quebracho accounts for 30% of the dry weight of the heartwoods with a worldwide production level averaging 177,000 tons per year over the past 30 years, according to the Tannin Corporation, Peabody, Mass. Tannins are commercially available and represent an inexpensive renewable resource.
  • This example describes carbon-metal nanocomposites from tannin-metal complexes, which are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 7 shows the X-Ray Diffractogram indicating the presence of elemental metal Nickel and carbon in the sample. Using the Scherrer equation, the crystallite size of the Ni—C nanocomposites was estimated to be 19 nm.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 8 shows a relationship between the temperature and microwave operating time, where the temperature increases when 1 g lignin is microwaved with 50 mg graphite powder and 50 mg carbon black powder in a 950 W microwave oven operating at 2.45 GHz. It is noted that the temperature of the sample in solid form reaches 1,000° C. in less than 6 minutes with a temperature (T) derivative over time (t), ⁇ T/ ⁇ t, which is the slope of the dotted curve shown in FIG. 8 , no less than 2.5° C./second at least for the first 360 seconds or several minutes (here about 6 minutes).
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 9 shows an XRD spectrum with distinctive peaks of carbon obtained from microwaving tannin according to one embodiment of the present invention, which are composed of a broad diffraction peak centered at about 20° 2 ⁇ (with a range of 17° and 22°) and another broad peak centered at about 44° 2 ⁇ .
  • the peak around 44° is due to nanodiamond. If the maximum intensity of the broad peak at about 20° is at 170 counts, the intensity of the peak at about 44° 2 ⁇ is about 70 counts.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 10 shows an XRD spectrum with distinctive peaks of carbon obtained from microwaving lignin according to one embodiment of the present invention, which are composed of a broad diffraction peak centered at about 21° 2 ⁇ (with a range of 18° and 24°) and another broad peak centered at about 44° 2 ⁇ .
  • the peak centered around 44° is due to nanodiamond. If the maximum intensity of the broad peak at about 20° is at 134 counts the intensity of the peak at about 44° 2 ⁇ is about 70 counts.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 11 shows an XRD spectrum for a carbon-nickel composite synthesized by microwaving a tannin-nickel complex according to one embodiment of the present invention, which includes a broad diffraction peak centered at about 21° 2 ⁇ (with a range of 17° and 24°) and other peaks centered at about 37.4 and 43.2° 2 ⁇ .
  • the peak at 43.2° is due to nanodiamond. If the maximum intensity of the broad peak at about 21° is at 110 counts, the intensity of the peak at about 43° 2 ⁇ is about 88 counts.
  • Sharp peaks at about 45°, about 52° and about 76° 2 ⁇ values represent the peaks due to Nickel nanoparticles, respectively.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 12 shows a Raman spectrum of carbon produced from microwaving tannin (without added carbon) according to one embodiment of the present invention.
  • the wavelength is followed by the intensity of the signal.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from tannin (in the absence of metal atoms or added carbon).
  • the broad peak that shows a maximum around 2700 cm ⁇ 1 may be ascribed to the first overtone of the band centered at 1333 cm ⁇ 1 .
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 13 shows a Raman spectrum of carbon produced from microwaving tannin (without added carbon) according to one embodiment of the present invention.
  • the wavelength is followed by the intensity of the signal.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from tannin (in the absence of metal atoms or added carbon).
  • the broad peak that shows a maximum around 2700 cm ⁇ 1 may be ascribed to the first overtone of the D band.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 14 shows a Raman spectrum of lignin produced by microwaving lignin (without added carbon) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from sodium salt of lignin (in the absence of metal atoms or added carbon).
  • the broad peak that shows a maximum around 2700 cm ⁇ 1 may be ascribed to the first overtone of the D band.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 15 shows a Raman spectrum of lignin produced by microwaving lignin (without added carbon) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from sodium salt of lignin (in the absence of metal atoms or added carbon).
  • the broad peak that shows a maximum around 2700 cm ⁇ 1 may be ascribed to the first overtone of the D band.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 16 shows a Raman spectrum of carbon produced from tannin-formaldehyde condensation product (no carbon added) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from microwaving (in the absence of metal atoms or added carbon) the reaction product of tannin and formaldehyde.
  • the broad peak that shows a maximum around 2700 cm ⁇ 1 may be ascribed to the first overtone of the D band.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 17 shows a Raman spectrum of carbon produced from tannin-formaldehyde condensation product (no carbon added) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from the reaction product of tannin and formaldehyde (in the absence of metal atoms or added carbon).
  • the broad peak that shows a maximum around 2700 cm ⁇ 1 may be ascribed to the first overtone of the D band.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 18 shows a Raman spectrum of carbon composite prepared by microwaving nickel-tannin composite (no carbon added) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from microwaving (in the absence of metal atoms or added carbon) the reaction product of tannin and nickel salt.
  • the measure of I G /I D intensity ratio is generally used as a measure of graphite ordering.
  • the broad peak that shows a maximum around 2700 cm ⁇ 1 may be ascribed to the first overtone of the D band.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 19 shows a Raman spectrum of carbon composite prepared by microwaving nickel-tannin composite (no carbon added) according to one embodiment of the present invention.
  • the frequency of signal is followed by intensity.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from microwaving (in the absence of metal atoms or added carbon) the reaction product of tannin and nickel salt.
  • the measure of I G /I D intensity ratio is generally used as a measure of graphite ordering.
  • the broad peak that shows a maximum around 2700 cm ⁇ 1 may be ascribed to the first overtone of the D band.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 20 shows a Raman spectrum of carbon composite prepared by microwaving iron (III)-lignosulfonate (no carbon added) according to one embodiment of the present invention. Number following frequency of signal (if shown) represents intensity.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from microwaving (in the absence of metal atoms or added carbon) the reaction product of lignosulfonate and ferric ion.
  • the broad peak that shows a maximum around 2700 cm ⁇ 1 may be ascribed to the first overtone of the D band.
  • This example describes carbon-metal nanocomposites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • FIG. 21 shows a Raman spectrum of carbon composite prepared by microwaving iron (III)-lignosulfonate (no carbon added) according to one embodiment of the present invention. Number following frequency of signal (if shown) represents intensity.
  • This figure shows a typical Raman spectroscopic data of carbon produced by the inventor in lab from microwaving (in the absence of metal atoms or added carbon) the reaction product of lignosulfonate and ferric ion.
  • This section provides various exemplary applications of the carbon and carbon-metal nano-composites that are synthesized according to one embodiment of the present invention utilizing the exemplary process set forth in EXAMPLE 1, or a process similar to it.
  • the transition metal phosphide materials that are synthesized according to one embodiment of the present invention may have a plethora of multi-functional applications including their use as catalysts in a variety of chemical reactions such as hydrodesulfurization and hydrodenitrogenation of petroleum feedstocks.
  • transition metal phosphide materials that are synthesized according to one embodiment of the present invention can be used in light emitting diodes.
  • transition metal phosphide materials that are synthesized according to one embodiment of the present invention can be used as lubricants.
  • transition metal phosphide materials that are synthesized according to one embodiment of the present invention can be used in lithium batteries.
  • transition metal phosphide materials that are synthesized according to one embodiment of the present invention can be used in thin film transistors.
  • transition metal phosphide materials that are synthesized according to one embodiment of the present invention can be used in high speed electronic devices.
  • Ni 2 P catalyst for simultaneous hydroprocessing (hydrodesulfurization and hydrodenitrogenation) of petroleum feedstocks (better than sulfided Mo/SiO 2 and Ni—Mo/SiO 2 currently used); useable as a material in modifying the physical properties of materials, corrosion resistant materials, wear-proof materials useable as a material in luminescent devices
  • Cu 3 P usable as a negative electrode material, fine solder and as an important alloy addition
  • Mn 2 P intercalates Li ion reversibly with low potential thus potentially being useful in fabricating Lithium batteries
  • FeP low bandgap semiconductor material with special magnetic properties.
  • GaP useable as a material to enhance scattering efficiency of visible light
  • MoP Hydroprocessing (Hydrodesulfurization and Hydrodenitrogenation) of organic compounds
  • the present invention provides a general method of preparation of nanoparticles of metals and metal derivatives containing metals in Groups III, IV, V, VI, VII, VIII, IB, IIB, IIIA of the Periodic Table. From the description set forth above, it is evident that the chemistries involved in the synthetic procedures according to the various embodiments of the present invention would be expected to be similar to that occurring during metal phosphide synthesis at least to a certain degree.
  • nickel phosphide nanoparticles that are synthesized according to various embodiments of the present invention either pristine, in a carbon composite or on a support such as a high surface area silica or alumina.
  • copper phosphide nanoparticles that are synthesized according to various embodiments of the present invention either pristine, in a carbon composite or on a support such as a high surface area silica or alumina.
  • Both nickel phosphide, and copper phosphide nanoparticles that are synthesized according to various embodiments of the present invention can be used as hydroprocessing catalysts.
  • hydroprocessing of crude oil containing S and N is of paramount importance to the oil industry.
  • Overall demand for petroleum refining catalysts is forecast to increase 2.8%/year, to $3.5 billion in 2010, according to a recent report by Ned Zimmerman, analyst at The Freedonia Group (Cleveland).
  • Hydroprocessing catalysts has been predicted to be the fastest-growing refinery catalysts due to increasingly higher sulfur-content oil (from future petroleum crude as well as Canadian tar sands).
  • the present invention in one aspect, relates to a process for synthesizing carbon-metal nanocomposites.
  • the process includes the steps of preparing a metal derivative or a metal chelated derivative of a carbon-containing precursor in solid form, and subjecting the metal derivative or metal chelated derivative of a carbon-containing precursor in solid form to microwave radiation at a frequency in the range of 900 MHz to 5.8 GHz, for a period of time effective to generate a heat flow from inside of the metal derivative or metal chelated derivative of a carbon-containing precursor in solid form to the outside such that the temperature of the metal derivative or metal chelated derivative of a carbon-containing precursor in solid form reaches 1,000° C. in less than 6 minutes with a temperature (T) derivative over time (t), ⁇ T/ ⁇ t, no less than 2.5° C./second to form carbon-metal nanocomposites.
  • T temperature
  • the frequency of microwave radiation is preferably at around 2.45 GHz, and the period of time effective is in a range of 30 seconds to 60 minutes, more preferably between 4 minutes and 30 minutes.
  • the metal of the metal derivative or metal chelated derivative is selected from the group consisting of Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au and a combination thereof.
  • the process in one embodiment, further has the step of performing an alkali treatment to the metal derivative or metal chelated derivative of a carbon-containing precursor prior to the subjecting step, wherein the metal in the metal derivative or metal chelated derivative is one of Co, Cu, Mn, Ni, Fe, W, Zr and Ti.
  • the carbon-containing precursor is selected from the group consisting of lignin, lignosulfonate, tannin, tanninsulfonate and sulfonated asphalt.
  • the subjecting step is performed in the presence of a microwave absorber.
  • the microwave absorber is selected from the group consisting of metal particles, phosphoric acid, hydrated NaH 2 PO 4 , CO 2 O 3 , CuO, MnO 2 , NiO, Fe 3 O 4 , WO 3 , Ag 2 O, Au 2 O 3 , non-stoichiometric oxides of titanium (TiO 2-x ) and a carbon allotrope, wherein the carbon allotrope is selected from the group consisting of carbon black, fullerene, graphite and carbon nanotubes.
  • the present invention in one aspect, also relates to carbon-metal nanocomposites made according to the process set forth above.
  • the present invention in another aspect, relates to a process for synthesizing carbon-metal nanocomposites.
  • the process includes the steps of preparing an ammonium salt of a carbon-containing precursor and a metal salt in solid form, and subjecting the ammonium salt of a carbon-containing precursor and the metal salt in solid form to microwave radiation at a frequency in the range of 900 MHz to 5.8 GHz, for a period of time effective to generate a heat flow from inside of the ammonium salt of a carbon-containing precursor and the metal salt in solid form to the outside such that the temperature of the ammonium salt of a carbon-containing precursor and the metal salt in solid form reaches 1,000° C. in about less than 6 minutes with a temperature (T) derivative over time (t), ⁇ T/ ⁇ t, no less than 2.5° C./second to form carbon-metal nanocomposites.
  • T temperature
  • the frequency of microwave radiation is preferably at around 2.45 GHz, and the period of time effective is in a range of 30 seconds to 60 minutes, more preferably between 4 minutes and 30 minutes.
  • the metal of the metal salt is selected from the group consisting of Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au and a combination thereof.
  • the metal salt is selected from the group consisting of an oxalate, an acetate, a sulfate and a chloride.
  • the carbon-containing precursor is selected from the group consisting of ammonium lignosulfonate, ammonium tanninsulfonate and ammonium asphaltsulfonate.
  • the subjecting step is performed in the presence of a microwave absorber.
  • the microwave absorber is selected from the group consisting of metal particles, phosphoric acid, hydrated NaH 2 PO 4 , CO 2 O 3 , CuO, MnO 2 , NiO, Fe 3 O 4 , WO 3 , Ag 2 O, Au 2 O 3 , non-stoichiometric oxides of titanium (TiO 2-x ) and a carbon allotrope, wherein the carbon allotrope is selected from the group consisting of carbon black, fullerene, graphite and carbon nanotubes.
  • the present invention in one aspect, also relates to carbon-metal nanocomposites made according to the process set forth above.
  • the present invention in another aspect, relates to a process for synthesizing carbon-metal nanocomposites.
  • the process includes the steps of preparing a carbon-containing precursor, and subjecting the carbon-containing precursor in the presence of a microwave absorber to microwave radiation at a frequency in the range of 900 MHz to 5.8 GHz, for a period of time effective to generate a heat flow from inside of the carbon-containing precursor to the outside such that the temperature of the carbon-containing precursor increases with a temperature (T) derivative over time (t), ⁇ T/ ⁇ t, no less than 2.5° C./second to form carbon-metal nanocomposites.
  • T temperature
  • the frequency of microwave radiation is preferably at around 2.45 GHz, and the period of time effective is in a range of 30 seconds to 60 minutes, more preferably between 4 minutes and 30 minutes.
  • the microwave absorber is selected from the group consisting of metal particles, phosphoric acid, hydrated NaH 2 PO 4 , CO 2 O 3 , CuO, MnO 2 , NiO, Fe 3 O 4 , WO 3 , Ag 2 O, Au 2 O 3 , non-stoichiometric oxides of titanium (TiO 2-x ) and a carbon allotrope, wherein the carbon allotrope is selected from the group consisting of carbon black, fullerene, graphite and carbon nanotubes.
  • the carbon-containing precursor is selected from the group consisting of lignin, an ammonium derivative of lignin, an alkali metal lignosulfonate, tannin, tanninsulfonate, asphalt, sulfonated asphalt, wood, sawdust, sucrose, lactose, cellulose, starch, polysaccharide, organic garbage, pitch derived from petroleum or coal, a carbon-containing polymer and their derivatives.
  • the carbon-containing polymer is selected from the group consisting of polyethylene glycol, polybenzimidazole, polybutadiene, polyethylene, polyvinyl alcohol, polyimides, polystyrene, rayon, polypropylene, nylon, phenol-formaldehyde resin and naphthalenesulfonic acid-formaldehyde copolymer.
  • the carbon-containing precursor further comprises a dispersion of a metal salt, wherein the metal of the metal salt is selected from the group consisting of Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au and a combination thereof.
  • the metal of the metal salt is selected from the group consisting of Sb, Li, Rb, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au and a combination thereof.
  • the process further includes the step of performing an alkali treatment to the metal salt prior to the subjecting step.
  • the present invention in one aspect, also relates to carbon-metal nanocomposites made according to the process set forth above.
  • the present invention in yet another aspect, relates to a process for synthesizing carbon-metal nanocomposites.
  • the process includes the steps of preparing a sample of metal ions and an organic compound, and subjecting the sample to microwave radiation at a frequency in the range of 900 MHz to 5.8 GHz, for a period of time effective to generate a heat flow from inside of the sample to the outside such that the temperature of the sample increases with a temperature (T) derivative over time (t), ⁇ T/ ⁇ t, no less than 2.5° C./second for at least several minutes to form carbon-metal nanocomposites.
  • the frequency of microwave radiation is preferably at around 2.45 GHz, and the period of time effective is in a range of 30 seconds to 60 minutes, more preferably between 4 minutes and 30 minutes.
  • the organic compound comprises one of cellulose, hydroxyalkylcellulose, cyclodextrins, chitin, chitosan, starch; guar gum and polysaccharides, wherein the hydroxyalkylcellulose comprises hydroxyethylcellulose, methylcellulose, and carboxymethylcellulose.
  • the metal ions comprises at least one of metals in Groups III, IV, V, VI, VII, VIII, IB, IIB, IIIA of the Periodic Table.
  • the present invention in one aspect, also relates to carbon-metal nanocomposites made according to the process set forth above.
  • the present invention in one aspect provides a method or process from which carbon-metal nanocomposites can be prepared by a novel microwave-assisted technique that will have tremendous implications in the synthesis of advanced nanocomposites from biomass and other suitable carbon precursors.
  • the process is simple yet on-obvious and occurs through a series of reactions initiated by a thermal runaway associated with the microwave absorption of the metal oxide, which in turn helps in the carbonization of lignin.
  • the carbon formed reduces the metal oxide to a metal resulting in a carbon-metal composite.
  • the method could be applied to a variety of different metals and is a powerful technique for generation of a plethora of carbon-metal nanocomposites from carbon-containing precursors.
  • the resulted carbon-metal nanocomposites, carbon nanoparticles, and metal nanoparticles can find many applications.

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US12/487,323 US20100035775A1 (en) 2008-06-18 2009-06-18 Microwave-assisted synthesis of carbon and carbon-metal composites from lignin, tannin and asphalt derivatives and applications of same
US12/751,185 US8647512B2 (en) 2008-06-18 2010-03-31 Use of magnetic carbon composites from renewable resource materials for oil spill clean up and recovery
PCT/US2010/029454 WO2011008315A1 (en) 2009-04-03 2010-03-31 Use of magnetic carbon composites from renewable resource materials for oil spill clean up and recovery
US12/754,336 US8920688B2 (en) 2008-06-18 2010-04-05 Microwave-assisted synthesis of transition metal phosphide
PCT/US2010/029978 WO2010115199A1 (en) 2009-04-03 2010-04-05 Microwave-assisted synthesis of transition metal phosphide
US13/069,097 US8790615B2 (en) 2008-06-18 2011-03-22 Methods of synthesizing carbon-magnetite nanocomposites from renewable resource materials and application of same
US13/069,057 US20110171108A1 (en) 2008-06-18 2011-03-22 Microwave-assisted synthesis of nanodiamonds from tannin, lignin, asphalt, and derivatives
US13/069,132 US8753603B2 (en) 2008-06-18 2011-03-22 Microwave-assisted synthesis of carbon nanotubes from tannin, lignin, and derivatives
US13/335,418 US8574337B2 (en) 2008-06-18 2011-12-22 Renewable resource-based metal-containing materials and applications of the same
US13/767,076 US9643165B2 (en) 2008-06-18 2013-02-14 Doped-carbon composites, synthesizing methods and applications of the same
US13/843,106 US9095837B2 (en) 2008-06-18 2013-03-15 Renewable resource-based metal oxide-containing materials and applications of the same
US14/134,992 US9169139B2 (en) 2008-06-18 2013-12-19 Use of magnetic carbon composites from renewable resource materials for oil spill clean up and recovery
US15/474,281 US10293329B2 (en) 2008-06-18 2017-03-30 Doped-carbon composites, synthesizing methods and applications of the same
US16/380,174 US10974230B2 (en) 2008-06-18 2019-04-10 Doped-carbon composites, synthesizing methods and applications of the same
US17/152,922 US12005429B2 (en) 2021-01-20 Doped-carbon composites, synthesizing methods and applications of the same

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US12/754,336 Continuation-In-Part US8920688B2 (en) 2008-06-18 2010-04-05 Microwave-assisted synthesis of transition metal phosphide
US13/069,057 Continuation-In-Part US20110171108A1 (en) 2008-06-18 2011-03-22 Microwave-assisted synthesis of nanodiamonds from tannin, lignin, asphalt, and derivatives
US13/069,132 Continuation-In-Part US8753603B2 (en) 2008-06-18 2011-03-22 Microwave-assisted synthesis of carbon nanotubes from tannin, lignin, and derivatives
US13/069,097 Continuation-In-Part US8790615B2 (en) 2008-06-18 2011-03-22 Methods of synthesizing carbon-magnetite nanocomposites from renewable resource materials and application of same
US13/335,418 Continuation-In-Part US8574337B2 (en) 2008-06-18 2011-12-22 Renewable resource-based metal-containing materials and applications of the same
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