WO2010107688A1 - Microspheres and their methods of preparation - Google Patents

Microspheres and their methods of preparation Download PDF

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Publication number
WO2010107688A1
WO2010107688A1 PCT/US2010/027293 US2010027293W WO2010107688A1 WO 2010107688 A1 WO2010107688 A1 WO 2010107688A1 US 2010027293 W US2010027293 W US 2010027293W WO 2010107688 A1 WO2010107688 A1 WO 2010107688A1
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microspheres
boron
carbon
doped
catalyst
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French (fr)
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Anima B. Bose
Junbing Yang
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Ohio University
UChicago Argonne LLC
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UChicago Argonne LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A61K9/1605—Excipients; Inactive ingredients
    • A61K9/1611—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
    • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
    • C01B3/0018—Inorganic elements or compounds, e.g. oxides, nitrides, borohydrides or zeolites; Solutions thereof
    • C01B3/0021—Elemental carbon, e.g. active carbon, carbon nanotubes or fullerenes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
    • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
    • C01B3/0084—Solid storage media characterised by their shape, e.g. porous compacts or hollow particles
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/36—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits
    • A61M1/3679—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits by absorption
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • 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
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • Y10S977/775—Nanosized powder or flake, e.g. nanosized catalyst
    • 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
    • Y10S977/902—Specified use of nanostructure
    • Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
    • 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
    • Y10S977/902—Specified use of nanostructure
    • Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
    • Y10S977/948—Energy storage/generating using nanostructure, e.g. fuel cell, battery
    • 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
    • Y10S977/902—Specified use of nanostructure
    • Y10S977/962—Specified use of nanostructure for carrying or transporting
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2989—Microcapsule with solid core [includes liposome]

Definitions

  • Carbon microspheres which generaily have a particle size less than about 700 nanometers, have a wide variety of potential applications. These microspheres can be used as catalyst supports, as a medium for storing hydrogen, and as adsorbants, such as in the case of hemoperfusion and ultrafiltration membranes. These microspheres are nanoporous particles which are prepared by chemical vapor deposition. However, their use is somewhat limited by a lack of activity, in particular, electrical conductivity.
  • the present invention is premised on the realization that boron-doped carbon microspheres can be prepared, and can be used in a wide variety of applications including nano wiring and integrated circuits, and have superior physical properties relative to carbon microspheres. - -
  • FIG. 1 is a graph of the BJH desorption differential pore volume distribution of boron-doped carbon microspheres (BCMS).
  • FlG. 2 is a diagrammatic depiction of a catalyst support.
  • FIG. 3 is a diagrammatic depiction of a hemoperfusion filter.
  • the boron-doped carbon microspheres of the present invention are microspheres having a diameter of less than about 700 nm and generally less than 500 nm, or less than 100 nm down to about 50 nm.
  • the microspheres are further considered to be nanoporous wherein the spheres include pores having a diameter generally in the range of 0.6 nm to about 2 nm
  • microspheres are formed from a combination of carbon and boron.
  • the major component of the microspheres is carbon.
  • the boron-doped carbon microspheres of the present invention are formed by chemical vapor deposition, in the chemical vapor deposition process, the reactants are injected into a flowing gas stream and are vaporized. The flowing gas stream, including the reactants, is heated further and impacted against a substrate and the carbon microspheres deposit on the substrate.
  • the reactants include a carbon source gas, a boron source, as well as a catalyst.
  • a catalyst any typical catalyst suitable for use in forming carbon microspheres can be employed. Iron, nickel and cobait catalysts can be used.
  • One typical catalyst is ferrocene.
  • the carbon source can be any hydrocarbon, either saturated or unsaturated and may be aromatic. In particular, compounds such as benzene and xylene are particularly suitable for use in the present invention as a carbon source.
  • the boron source must be a compound that can be formed into a vapor at reaction temperatures without decomposing. Generally, a vapor is formed by dissolving a boron containing compound into an appropriate solvent, preferably a hydrocarbon solvent, and then injecting this into the chemical vapor deposition - - reactor. As is described below, it is convenient to dissolve the boron source into the carbon source.
  • Suitable boron containing compounds inciude the halides, such as boron trifiouride and boron trichloride, as well as other compounds that can be dissolved in an appropriate solvent such as nitrates, and the like.
  • the stoichiometric ratio of boron to carbon wiil be 1 to 20 to 1 .5 to 10 generally 1 to 9 to
  • the reaction is conducted in a chemical vapor deposition reactor with a suitable deposition substrate.
  • the deposition substrate must be inert under reaction conditions.
  • Suitable substrates include magnesium oxide, aluminum oxide, indium tin oxide, as well as quartz.
  • Chemical vapor deposition reactors include a heating zone and a reaction zone. To form the microspheres, the heating zone is maintained at a temperature sufficient to vaporize the reactants, typically about 200 0 C. The reaction zone is maintained at a much higher temperature, generally above 650 0 C for this reaction, typically about 850-1000 °C. The reaction is conducted by forming a solution of the reactants, including the catalyst, carbon source and boron source, in the desired stoichiometric relation. This is injected into the heating zone into a flowing gas stream.
  • the flowing gas stream can be a variety of inert gases, but typically are nitrogen or argon, or mixtures thereof. Hydrogen may also be included to avoid soot formation, if needed. Further, a nitrogen source gas such as ammonia may be added to facilitate boron inclusion into the microspheres.
  • ammonia If added, it will generally comprise about 10% of the partial pressure of the gas stream. Hydrogen w ⁇ l comprise 0-20% of the partial pressure of the gas stream. Generally, the ratio of ammonia to hydrogen to inert gas (Ar) will vary from 1 :1 :1 : to 1 :4:4 by volume.
  • the flowing gas stream draws the reactants from the heating zone where they are vaporized into the reaction zone where they form the boron-doped carbon microspheres on the selected substrate, typically quartz.
  • the reactor is purged with an inert gas to remove all oxygen from the system prior to the reaction. After purging, the flow of gas is started. The reactants are then introduced in the desired ratio into the flowing gas stream. After an appropriate period of time, generally 5 minutes to 1 hour, the injection of the reactants is discontinued and the furnace cooled down to room temperature under argon and hydrogen.
  • the formed microspheres can be subjected to a mild oxidation in order to open the porous structure.
  • the preheating zone is heated to a temperature of about 500 0 C, and the reaction zone to about 850 0 C.
  • Deionized water is simply injected into the preheating zone and evaporated and transported into the reaction zone in flowing argon. This is continued again for about 30 minutes.
  • the furnace is then cooled down to room temperature under flowing argon.
  • BCMS Boron-doped carbon microspheres
  • Example 1 The boron-doped carbon microspheres (BCMS) formed in Example 1 were activated in steam to open the pore structure.
  • Zone I and Zone Il were heated and kept at 500 0 C and 850 0 C, respectively.
  • Deionized water was injected into and evaporated inside the quartz tube in the middle of Zone I at the rate of 0.225 ml/min.
  • Flowing argon 140 ml/min was used to carry the steam to -o-
  • the injection of water lasted for 30 minutes. After stopping the injection of water and turning off the temperature controller, the furnace was cooled down to room temperature with flowing argon.
  • the boron-doped carbon microspheres formed from the above examples were spherical particles with uniform particle size. TEM images reveal that the microspheres have an onion structure, and x-ray photon electron spectrum indicated they are comprised of carbon, boron and oxygen an impurity. Generally, the boron to carbon ratio is approximately from 1 :4 - 1 :12. [ ⁇ 027J The microspheres are high purity uniform spheres of about 700 nanometers or less in diameter, and reasonably high surface area of about 220 m 2 /g measured via nitrogen absorption.
  • thermogravimetric analysis demonstrates that the oxidation stability is comparable to pure multiwall nanotubes.
  • the activated microspheres contain a large number of mesopores and the BET surface area is about 213 m 2 /g, which is the same range as standard carbon black, but higher than muStiwaSI carbon nanotubes.
  • the sheet resistance of the microspheres is lower than that formed from multiwalled carbon nanotubes.
  • the micropore surface area was 107 m 2 /g and the total pore volume was 0.163 cm 3 /g.
  • the micropore volume was 0.054 cm 3 /g and the median micropore diameter was 0.62 nm.
  • Fig. 1 shows the pore size distribution of the activated mircospheres.
  • the activated microspheres clearly contain a large number of mesospheres.
  • the boron-doped carbon microspheres of the present invention can be used in a variety of different applications. Sn particular, these can be used in fuel cells, which are devices that convert chemical energy of fuels, such as hydrogen, directly into electrical energy.
  • the proton exchange membrane fuel cell is one type of fuel cell that can utilize the boron-doped carbon microspheres of the present invention.
  • the boron-doped carbon microspheres can be used in any fuel ceil operating at less than 500 0 C. These can be combined with an electron conducting resin or used on other supports.
  • the boron-doped carbon microspheres of the present invention can provide a durable catalyst support.
  • the uniform pore size of the microspheres allow the microspheres to carry gases through their porous structure.
  • the unique spherical structure and high thermal stability and oxidation resistance of the boron-doped carbon microspheres compared to carbon black, carbon fibers or carbon nanotubes enable this product to be used as a catalyst support in which its uniform rate of gas transport does not degrade.
  • the microspheres can be used as supports for electrolytic cell cathodes or anodes. These would be used in the electrolysis of water, ammonia or dissolved organic material.
  • the catalyst support can take the configuration shown in FIG.
  • a porous conductive support layer 11 is coated with a layer 12 of the boron- doped carbon nanospheres.
  • This layer is in turn coated with a catalyst 13 such as a noble metal.
  • the catalyst can be deposited by well known methods such as vapor deposition, electrochemical deposition and chemical deposition.
  • Exemplary catalysts include platinum, iridium, ruthenium, rhenium, palladium, gold, silver, nickel, iron, lanthanides and alloys of these. Basically, any catalyst can be supported by these microspheres, including nonmetallic catalysts as well as metallic catalysts.
  • the boron-doped carbon microspheres of the present invention can also be used as an adsorbant to store gases such as hydrogen.
  • gases such as hydrogen
  • hydrogen is typically stored under elevated pressure, and frequently at reduced temperatures, causing the hydrogen to migrate into the boron-doped carbon microspheres.
  • the boron in particular, enhances the hydrogen absorption via a non-classical chemical binding mechanism in which the two undissociated H atoms in the molecule and the B form a 3-body center sharing two common electrons. Further the high surface area increase H 2 absorption.
  • the microspheres of the present invention can be used as a drug delivery system, absorbing pharmacologically active organic compounds, and gradually releasing them subsequent to administration.
  • the boron-doped carbon microspheres of the present invention can be used as adsorbents in a wide variety of different applications, and, in particular, in hemoperfusion applications.
  • the hemoperfusion filter 20 would include a porous support layer 22 coated with a layer of the boron-doped carbon microspheres 24, Blood or other fluid would flow through the filter 20 in the direction of arrow 26. Organic molecules will tend to bond to the microspheres thereby filtering the fluid.
  • the boron-doped carbon microspheres possess a much higher electrical conductivity than carbon nanotubes while being stable at higher temperatures. For that reason, the microspheres can be used in a variety of different applications.
  • microspheres are particularly useful in batteries as a conductive surface and/or support.
  • the microspheres can form conductive surfaces in metal ion batteries as well as metal hydride batteries and other batteries such as metal/air batteries.
  • These microspheres can also replace carbon in the cathodes and anodes in batteries, fuel cells and electrolytic cells. They can also comprise nonometer size conductors or nano wiring for micro circuits.
  • the boron-doped carbon microspheres can be used in any application requiring electrical conductivity, and, in particular can be used to replace indium tin oxide in a variety of different applications, including solar panels, and the like.
  • the boron-doped carbon microspheres can be added to photoactive compositions and used to form thin layer solar panels.
  • the boron-doped carbon microspheres of the present invention can be used in a wide variety of different applications because of their enhanced support stability through boron doping, enhanced catalyst support interaction providing improved stability, high electronic conductivity, spherical particie shape permitting uniform packing density. [0041] This has been a description of the present invention along with the preferred method of practicing the present invention. However, the invention itself should only be defined by the appended claims, WHEREIN WE CLAIM:

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Abstract

Carbon microspheres are doped with boron to enhance the electrical and physical properties of the microspheres. The boron-doped carbon microspheres are formed by a CVD process in which a catalyst, carbon source and boron source are evaporated, heated and deposited onto an inert substrate.

Description

MICROSPHERES AND THEIR METHODS OF PREPARATION
GOVERNMENT RIGHTS
[0001] This invention was made with Government support under Contract No.
DE-AC02-06CH1 1357, awarded by the US Department of Energy, and Contract SL-26-7006-01 05P 08-282 awarded by the Department of Transportation. The Government has certain rights in this invention.
RELATED APPLICATION
[0002] This application is related to and claims the benefit of U.S. Provisional
Patent Application Serial No. 61/161 ,580, filed March 19, 2009, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0003] Carbon microspheres, which generaily have a particle size less than about 700 nanometers, have a wide variety of potential applications. These microspheres can be used as catalyst supports, as a medium for storing hydrogen, and as adsorbants, such as in the case of hemoperfusion and ultrafiltration membranes. These microspheres are nanoporous particles which are prepared by chemical vapor deposition. However, their use is somewhat limited by a lack of activity, in particular, electrical conductivity.
SUMMARY OF THE INVENTION
[0004] The present invention is premised on the realization that boron-doped carbon microspheres can be prepared, and can be used in a wide variety of applications including nano wiring and integrated circuits, and have superior physical properties relative to carbon microspheres. - -
[0005] The objects and advantages of the present invention will be further appreciated in light of the following detailed description and drawing in which:
BRIEF DESCRIPTION OF DRAWING
[00061 FIG. 1 is a graph of the BJH desorption differential pore volume distribution of boron-doped carbon microspheres (BCMS). [0007] FlG. 2 is a diagrammatic depiction of a catalyst support.
[0008] FIG. 3 is a diagrammatic depiction of a hemoperfusion filter.
DETAILED DESCRIPTION
[ΘΘ09] The boron-doped carbon microspheres of the present invention are microspheres having a diameter of less than about 700 nm and generally less than 500 nm, or less than 100 nm down to about 50 nm. The microspheres are further considered to be nanoporous wherein the spheres include pores having a diameter generally in the range of 0.6 nm to about 2 nm
[0010] These microspheres are formed from a combination of carbon and boron. The major component of the microspheres is carbon. The boron-doped carbon microspheres of the present invention are formed by chemical vapor deposition, in the chemical vapor deposition process, the reactants are injected into a flowing gas stream and are vaporized. The flowing gas stream, including the reactants, is heated further and impacted against a substrate and the carbon microspheres deposit on the substrate.
[0011] The reactants include a carbon source gas, a boron source, as well as a catalyst. Generally, any typical catalyst suitable for use in forming carbon microspheres can be employed. Iron, nickel and cobait catalysts can be used. One typical catalyst is ferrocene.
[0012] The carbon source can be any hydrocarbon, either saturated or unsaturated and may be aromatic. In particular, compounds such as benzene and xylene are particularly suitable for use in the present invention as a carbon source. [0013] The boron source must be a compound that can be formed into a vapor at reaction temperatures without decomposing. Generally, a vapor is formed by dissolving a boron containing compound into an appropriate solvent, preferably a hydrocarbon solvent, and then injecting this into the chemical vapor deposition - - reactor. As is described below, it is convenient to dissolve the boron source into the carbon source.
[0014] Suitable boron containing compounds inciude the halides, such as boron trifiouride and boron trichloride, as well as other compounds that can be dissolved in an appropriate solvent such as nitrates, and the like. Generally, the stoichiometric ratio of boron to carbon wiil be 1 to 20 to 1 .5 to 10 generally 1 to 9 to
1 to 10.
[0015] The reaction is conducted in a chemical vapor deposition reactor with a suitable deposition substrate. The deposition substrate must be inert under reaction conditions. Suitable substrates include magnesium oxide, aluminum oxide, indium tin oxide, as well as quartz.
[0016] Chemical vapor deposition reactors include a heating zone and a reaction zone. To form the microspheres, the heating zone is maintained at a temperature sufficient to vaporize the reactants, typically about 200 0C. The reaction zone is maintained at a much higher temperature, generally above 650 0C for this reaction, typically about 850-1000 °C. The reaction is conducted by forming a solution of the reactants, including the catalyst, carbon source and boron source, in the desired stoichiometric relation. This is injected into the heating zone into a flowing gas stream.
[0017] The flowing gas stream can be a variety of inert gases, but typically are nitrogen or argon, or mixtures thereof. Hydrogen may also be included to avoid soot formation, if needed. Further, a nitrogen source gas such as ammonia may be added to facilitate boron inclusion into the microspheres.
[0018] If ammonia is added, it will generally comprise about 10% of the partial pressure of the gas stream. Hydrogen wϋl comprise 0-20% of the partial pressure of the gas stream. Generally, the ratio of ammonia to hydrogen to inert gas (Ar) will vary from 1 :1 :1 : to 1 :4:4 by volume. The flowing gas stream draws the reactants from the heating zone where they are vaporized into the reaction zone where they form the boron-doped carbon microspheres on the selected substrate, typically quartz.
[0019] When the nitrogen source gas, ammonia, is added, it is believed that the nitrogen bonds to carbon and bonds to the boron. If ammonia is not present, the boron bonds directly to the carbon. This latter reaction is not as thermodynamicalty favored as the nitrogen carbide formation. Thus, the addition of ammonia increases the incorporation of boron into the microspheres. ~ -
[0020] Typically, the reactor is purged with an inert gas to remove all oxygen from the system prior to the reaction. After purging, the flow of gas is started. The reactants are then introduced in the desired ratio into the flowing gas stream. After an appropriate period of time, generally 5 minutes to 1 hour, the injection of the reactants is discontinued and the furnace cooled down to room temperature under argon and hydrogen.
[00211 The formed microspheres can be subjected to a mild oxidation in order to open the porous structure. In order to do so, the preheating zone is heated to a temperature of about 500 0C, and the reaction zone to about 850 0C. Deionized water is simply injected into the preheating zone and evaporated and transported into the reaction zone in flowing argon. This is continued again for about 30 minutes. The furnace is then cooled down to room temperature under flowing argon.
[0022] The invention will be further appreciated in light of the following detailed examples.
EXAMPLE 1 : Synthesis of BCMS
[0023] Boron-doped carbon microspheres (BCMS) were prepared by a chemical vapor deposition process inside a quartz tube inserted through a low- temperature heating section (Zone I, 200 0C) and a high-temperature heating section (Zone Ii, 950 0C).
[0024] 0.34 g Ferrocene was dissolved in 23.63 g boron trichloride solution
1 .0 M in p-xylene (both from Sigma-Aldrich) and used as precursor for BCMS synthesis. The solution was injected and vaporized in Zone I. A hydrogen and argon mixture (60 ml/min and 90 ml/min, respectively) was used to transport the vapor from Zone I to Zone II. The BCMS were formed over a polished quartz plate inside Zone II. After 30 minutes, the solution injection was stopped and the furnaces were cooled down to room temperature with the argon and hydrogen flowing.
EXAMPLE 2: Activation of BCMS
[0025] The boron-doped carbon microspheres (BCMS) formed in Example 1 were activated in steam to open the pore structure. For this purpose, Zone I and Zone Il were heated and kept at 5000C and 8500C, respectively. Deionized water was injected into and evaporated inside the quartz tube in the middle of Zone I at the rate of 0.225 ml/min. Flowing argon (140 ml/min) was used to carry the steam to -o-
Zone I! and react with BCMS, which were synthesized as disclosed in Example 1 . The injection of water lasted for 30 minutes. After stopping the injection of water and turning off the temperature controller, the furnace was cooled down to room temperature with flowing argon.
[0026] The boron-doped carbon microspheres formed from the above examples were spherical particles with uniform particle size. TEM images reveal that the microspheres have an onion structure, and x-ray photon electron spectrum indicated they are comprised of carbon, boron and oxygen an impurity. Generally, the boron to carbon ratio is approximately from 1 :4 - 1 :12. [Θ027J The microspheres are high purity uniform spheres of about 700 nanometers or less in diameter, and reasonably high surface area of about 220 m2/g measured via nitrogen absorption.
[0028] Further, thermogravimetric analysis demonstrates that the oxidation stability is comparable to pure multiwall nanotubes. The activated microspheres contain a large number of mesopores and the BET surface area is about 213 m2/g, which is the same range as standard carbon black, but higher than muStiwaSI carbon nanotubes. The sheet resistance of the microspheres is lower than that formed from multiwalled carbon nanotubes. The micropore surface area was 107 m2/g and the total pore volume was 0.163 cm3/g. The micropore volume was 0.054 cm3/g and the median micropore diameter was 0.62 nm. Fig. 1 shows the pore size distribution of the activated mircospheres. The activated microspheres clearly contain a large number of mesospheres.
EXAMPLE 3: Incorporation of Nitrogen
[0029] 0.5 g Ferrocene was dissolved in 28.0 g boron trichloride solution in
1.0 M p-xyiene {both from Sigma-Aldrich) and used as precursor for BCMS synthesis. The solution was injected into the same reactor as in Example 1 and fully vaporized in the low-temperature zone I (200 0C). A carrier gas mixture containing ammonia, hydrogen and argon with pre-set volume ratio (volume ratio NH3/Hs/Ar = 1/1.33/4 and total flow rate of 190 ml/min) was added through upstream of zone I. BCMS formed on the surface of a quartz substrate positioned in the high- temperature zone at 900 0C. The growth process tasted for 30 minutes until the liquid precursor injection stopped. The carrier gas continued to flow for another 20 minutes before the reactor was cooled down. - -
[0030J The boron-doped carbon microspheres of the present invention can be used in a variety of different applications. Sn particular, these can be used in fuel cells, which are devices that convert chemical energy of fuels, such as hydrogen, directly into electrical energy. The proton exchange membrane fuel cell is one type of fuel cell that can utilize the boron-doped carbon microspheres of the present invention. The boron-doped carbon microspheres can be used in any fuel ceil operating at less than 500 0C. These can be combined with an electron conducting resin or used on other supports.
[0031] Also, the boron-doped carbon microspheres of the present invention can provide a durable catalyst support. The uniform pore size of the microspheres allow the microspheres to carry gases through their porous structure. In particular, the unique spherical structure and high thermal stability and oxidation resistance of the boron-doped carbon microspheres compared to carbon black, carbon fibers or carbon nanotubes, enable this product to be used as a catalyst support in which its uniform rate of gas transport does not degrade. Thus, the microspheres can be used as supports for electrolytic cell cathodes or anodes. These would be used in the electrolysis of water, ammonia or dissolved organic material. [0032] The catalyst support can take the configuration shown in FIG. 2 in which a porous conductive support layer 11 is coated with a layer 12 of the boron- doped carbon nanospheres. This layer is in turn coated with a catalyst 13 such as a noble metal. The catalyst can be deposited by well known methods such as vapor deposition, electrochemical deposition and chemical deposition. Exemplary catalysts include platinum, iridium, ruthenium, rhenium, palladium, gold, silver, nickel, iron, lanthanides and alloys of these. Basically, any catalyst can be supported by these microspheres, including nonmetallic catalysts as well as metallic catalysts.
[0033] The boron-doped carbon microspheres of the present invention can also be used as an adsorbant to store gases such as hydrogen. In this application, hydrogen is typically stored under elevated pressure, and frequently at reduced temperatures, causing the hydrogen to migrate into the boron-doped carbon microspheres. The boron, in particular, enhances the hydrogen absorption via a non-classical chemical binding mechanism in which the two undissociated H atoms in the molecule and the B form a 3-body center sharing two common electrons. Further the high surface area increase H2 absorption. [0034] Also, due to the ability of the microspheres to absorb organic compounds, the microspheres of the present invention can be used as a drug delivery system, absorbing pharmacologically active organic compounds, and gradually releasing them subsequent to administration.
[0035] In another application, the boron-doped carbon microspheres of the present invention can be used as adsorbents in a wide variety of different applications, and, in particular, in hemoperfusion applications. The uniform size of these spheres, along with their porous structure, both facilitate in use in hemoperfusion in place of activated carbon.
[0036] As shown in FIG 2, the hemoperfusion filter 20 would include a porous support layer 22 coated with a layer of the boron-doped carbon microspheres 24, Blood or other fluid would flow through the filter 20 in the direction of arrow 26. Organic molecules will tend to bond to the microspheres thereby filtering the fluid. [0037] The boron-doped carbon microspheres possess a much higher electrical conductivity than carbon nanotubes while being stable at higher temperatures. For that reason, the microspheres can be used in a variety of different applications.
[0038] These microspheres are particularly useful in batteries as a conductive surface and/or support. The microspheres can form conductive surfaces in metal ion batteries as well as metal hydride batteries and other batteries such as metal/air batteries. These microspheres can also replace carbon in the cathodes and anodes in batteries, fuel cells and electrolytic cells. They can also comprise nonometer size conductors or nano wiring for micro circuits.
[0039] The boron-doped carbon microspheres can be used in any application requiring electrical conductivity, and, in particular can be used to replace indium tin oxide in a variety of different applications, including solar panels, and the like. In particular, the boron-doped carbon microspheres can be added to photoactive compositions and used to form thin layer solar panels.
[0040] Thus, the boron-doped carbon microspheres of the present invention can be used in a wide variety of different applications because of their enhanced support stability through boron doping, enhanced catalyst support interaction providing improved stability, high electronic conductivity, spherical particie shape permitting uniform packing density. [0041] This has been a description of the present invention along with the preferred method of practicing the present invention. However, the invention itself should only be defined by the appended claims, WHEREIN WE CLAIM:

Claims

- - WHAT IS CLAIMED IS:
1 . Carbon microspheres having an average diameter of less than 700 nm wherein microspheres are doped with boron,
2. The carbon microspheres claimed in claim 1 wherein the boron to carbon ratio of said microspheres is at Seast 1 :20.
3. The carbon microspheres claimed In claim 2 wherein the boron to carbon ratio of said carbon microspheres is less than 1 .5 to 10.
4. The carbon microspheres claimed in claim 3 wherein the boron to carbon ratio of said microspheres is from about 1 :4 - 1 :12.
5. The carbon microspheres claimed in claim 1 further comprising nitrogen.
6. A separator for an electrolytic ceil comprising a support containing the carbon microspheres ciaimed in claim 1 .
7. A method of forming boron-doped carbon microspheres comprising heating a carbon source and a boron source and a catalyst in a gas stream to a temperature effective to vaporize said sources and said catalyst thereby forming a reactant vapor mixture; and further heating said vapor mixture to a second temperature effective to cause said boron source and said carbon source to react and depositing boron- doped microspheres onto a substrate.
8. The method claimed in claim 7 wherein said gas stream comprises one of H2, N2, Ar, and mixtures thereof,
9. The method claimed in claim 7 wherein said gas stream further includes NH3. - -
10. The method claimed in claim 7 further comprising contacting said microspheres with steam to activate said microspheres.
1 1 . The microspheres claimed in claim 1 further comprising a gas stored in said microspheres.
12. The microspheres claimed in claim 1 1 wherein said gas is H2.
13. A fuel ceil including a membrane; said membrane comprising an electron conducting resin in combination with boron-doped carbon microspheres.
14. A catalyst structure comprising a layer of boron-doped carbon microspheres coated with a cataiyst.
15. The catalyst structure claimed in claim 13 wherein said catalyst is a metal.
16. The catalyst structure claimed in claim 14 wherein said structure is an electrode in an electrolytic ceil.
17. A method of storing H2 with boron-doped carbon microspheres at superatmospheric pressure and at subambient temperatures, thereby causing said H2 to be absorbed into said microspheres.
18. A hemoperfusion device having a filter; said filter comprising a layer of boron-doped carbon microspheres supported on a porous substrate.
19. A delayed release composition comprising an active pharmaceutical composition adsorbed onto a boron-doped carbon microsphere.
20. A photovoltaic device comprising a layer comprising a photoactive composition adsorbed onto boron-doped carbon microspheres.
21. An electrical conductor formed from carbon microspheres claimed in claim 1.
22. The electrical conductor claimed in claim 21 wherein said conductor is in a battery.
23. The electrical conductor claimed in claim 22 wherein said conductor is an electrode.
24. The electrical conductor claimed in claim 21 wherein said conductor comprises nano wiring.
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