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WO2012016296A1 - Procédés de préparation de nanoparticules à base de carbogène et nanoparticules photoluminescentes à base de carbogène - Google Patents

Procédés de préparation de nanoparticules à base de carbogène et nanoparticules photoluminescentes à base de carbogène Download PDF

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WO2012016296A1
WO2012016296A1 PCT/AU2011/000998 AU2011000998W WO2012016296A1 WO 2012016296 A1 WO2012016296 A1 WO 2012016296A1 AU 2011000998 W AU2011000998 W AU 2011000998W WO 2012016296 A1 WO2012016296 A1 WO 2012016296A1
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carbogenic
nanoparticles
precursor material
acid
photoluminescent
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Qin Li
Fu Wang
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Curtin University
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Curtin University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to methods for preparing carbogenic nanoparticles and photoluminescent carbogenic nanoparticles.
  • Luminescent semiconductor quantum dots are nanoparticles with size dependent optical and electronic properties. They have been the subject of intensive research and development for a broad range of applications such as energy-efficient displays and lighting, photovoltaic devices, and biological markers. However, the intrinsic toxicity and potential environmental hazards associated with many of these nanomaterials represent considerable challenges to their practical usage. Light- emitting quantum-sized carbon dots (CDs) appears to be a promising alternative to semiconductor QDs in many of the applications owing to their low toxicity and cheaper cost.
  • CDs quantum-sized carbon dots
  • quantum-sized carbon nanoparticles Following the development of the laser ablation method for preparation of quantum- sized carbon nanoparticles, various methods have been developed to produce quantum-sized carbon nanoparticles. Some of these methods include electrochemical release or exfoliation from a graphitic source, separation of combusted carbon soot, carbonizing polymerized resols on silica spheres, and thermal oxidation of suitable molecular precursors.
  • the invention provides a method for preparing carbogenic nanoparticles comprising carbonizing a carbogenic precursor material in a high boiling point solvent.
  • carbonizing the carbogenic precursor material comprises contacting the carbogenic precursor material with the high boiling point solvent at an elevated temperature.
  • the elevated temperature may be in a range of about 120 °C to about 300 °C, preferably from about 140 °C to about 280 °C.
  • the method comprises carbonizing the carbogenic precursor substance in the high boiling point solvent in the presence of an acid.
  • carbogenic nanoparticles prepared in accordance with the first aspect of the invention may be inherently photoluminescent. The quantum yield of such carbogenic nanoparticles may be enhanced by preparing such carbogenic nanoparticles in accordance with the first aspect of the invention in the presence of a surface passivating agent.
  • the carbogenic nanoparticles of the present invention may be rendered photoluminescent by passivating the surface of the carbon nanoparticle.
  • passivating the carbogenic nanoparticles may be achieved by treating the carbogenic nanoparticles with a surface passivating agent after the carbogenic nanoparticles have been prepared according to the first aspect of the invention.
  • preparing photoluminescent carbogenic nanoparticles may be achieved by treating a carbogenic precursor material with an acid in a high boiling point solvent in the presence of a surface passivating agent.
  • the method of the present invention is capable of preparing photoluminescent carbogenic nanoparticles in the absence of a surface passivating agent or without treating the surface of the carbogenic nanoparticles with a surface passivating agent.
  • a second aspect of the invention provides carbogenic nanoparticles comprising a core of carbogenic material, the carbogenic material comprising a plurality of fluorophores located in or on the core.
  • the carbogenic nanoparticles are photoluminescent under excitation by near infrared frequencies. Photoluminescence may be induced by a two-photon absorption process.
  • the nanoparticle has a particle size in a range of about 0.1 nm to about 10 nm.
  • the nanoparticles have a uniform particle size with a particle size distribution range of about 1 nm to about 2 nm.
  • the invention provides photoluminescent carbogenic nanoparticles comprising a core of nitrogen enriched-carbogenic material.
  • Figure 1 is a photograph of the toluene solution of Oil soluble' photoluminescent carbon nanoparticles prepared in accordance with one embodiment of the present invention after 180 min reaction excited by the fiber of the fluorescent spectrometer (A), and the absorption and photoluminescence emission spectra of the photoluminescent carbon nanoparticles reacted after (B) 5 min (C) 180min.
  • Figure 2 is an absorption and photoluminescence emission spectra of the 'water soluble' photoluminescent carbon nanoparticles prepared in accordance with one embodiment of the present invention when reacted after (A) 5 min (B) 180 min.
  • Figure 3 is a representation of the temporal evolution of the absorption and normalized photoluminescent spectra of Oil soluble' photoluminescent carbon nanoparticles shown in Figure 1 pyrolyzed in 1 -octadecylene (A), and the relationship between quantum yield and reaction time (B) excited at 360nm and 420nm using Quinine sulfate in 0.1 M H 2 S0 4 and Coumarin 6 in ethanol as standard references, respectively.
  • A 1 -octadecylene
  • B quantum yield and reaction time
  • Figure 4 is a representation of the temporal evolution of the absorption and normalized photoluminescent spectra of 'water soluble' photoluminescent carbon nanoparticles shown in Figure 2 pyrolyzed in glycerin (A), and relationship between quantum yield and reaction time (B) excited at 360nm and 420nm using Quinine sulfate in 0.1 M H 2 S0 4 and Coumarin 6 in ethanol as standard references, respectively.
  • Figure 5 are TEM images (200 keV) and AFM topography images on mica substrates of 'oil soluble' photoluminescent carbon nanoparticles prepared in accordance with an embodiment of the present invention reacted after 5 min (A) (B) and after 180 min(C) (D).
  • Figure 6 is a TEM and AFM image of 'oil soluble' photoluminescent carbon nanoparticles prepared in accordance with an embodiment of the present invention.
  • Figure 7 is a TEM and AFM image of carbon nanoparticles prepared in accordance with another embodiment of the present invention.
  • Figure 8 is the absorption and photoluminescence emission spectra of carbon nanoparticles prepared in accordance with another embodiment of the present invention.
  • Figure 9 is a series of FT-IR spectra of citric acid (a); carbon nanoparticles (b);
  • OCDs oil soluble' photoluminescent carbon nanoparticles
  • WCDs water soluble' photoluminescent carbon nanoparticles
  • Figure 10 are powder XRD patterns of 'oil soluble' photoluminescent carbon nanoparticles (OCDs) and 'water soluble' photoluminescent carbon nanoparticles (WCDs).
  • Figure 1 1 (a) is a UV-visible absorption spectrum of the three fractions nitrogen enriched carbogenic nano-particles referred to as ⁇ 1 K, 1 K, and 3.5K in Example 7; and Figures 1 1 (b)-1 1 (d) are a series of photoluminescence emission spectra for the three fractions referred to as ⁇ 1 K, 1 K, and 3.5K, respectively, where the excitation wavelength was step-wise increased from 330 nm to 450 nm.
  • Figure 12 is a series of FTI spectra of several carbogenic precursor materials and carbogenic nanoparticles prepared in accordance with the present invention from said carbogenic precursor materials.
  • Figure 13 is an excitation-emission spectrum of nitrogen enriched-carbogenic nanoparticles prepared in accordance with the present invention, wherein excitation is by wavelength longer than 700 nm.
  • the present application relates to methods for preparing carbogenic nanoparticles and photoluminescent carbogenic nanoparticles, respectively.
  • the term 'carbogenic nanoparticle' is used to refer to nanoparticles substantially comprising a carbon-based material.
  • carbon-based materials include, but are not limited to, amorphous carbon, semi-crystalline carbon, crystalline carbon, graphitic carbon, graphene-like carbon, carbogenic compounds, and carbogenic oligomers.
  • the carbon-based material may be doped or enriched with heteroatoms, such as N, B, S, F, O, P, Si and so forth, by using a carbogenic precursor material which contains said heteroatoms.
  • the carbon content of the carbogenic nanoparticle may be at least 40 wt%.
  • the carbogenic nanoparticles prepared in accordance with the methods of the present invention may have a particle size in a range of about 0.1 nm to about 10 nm. Generally, said nanoparticles have a substantially uniform particle size with a particle size distribution range of about 1 nm to about 2 nm.
  • photoluminescent carbon nanoparticles have been prepared. These photoluminescent carbon nanoparticles comprise a carbon core and a passivation agent coupled to the carbon core.
  • the carbon core component may be produced via laser ablation of a graphite powder carbon target or by electric arc discharge from carbon powders.
  • the passivation agent is then subsequently bound to the surface of the carbon core by known techniques. Excitation energy traps existing at the surface of the carbon core are stabilized by the passivation agent that is coupled to the carbon core, thereby rendering the carbon nanoparticle photoluminescent.
  • carbogenic nanoparticles prepared according to the present invention may be photoluminescent in the absence of a surface passivating agent.
  • These photoluminescent carbogenic nanoparticles comprise a core of carbogenic material, wherein the carbogenic material comprises a plurality of fluorophores located in or on the core.
  • the inventors have speculated that the fluorophores may be formed during carbonization of the carbogenic precursor material, and that the incidence of fluorophores located in or on the core may be enhanced (and therefore the photoluminescence of the carbongenic nanoparticles may be enhanced) by carbonizing the carbogenic precursor material in the presence of an acid and/or a surface passivating agent.
  • the fluorophores include, but are not limited to, polyaromatic fluorophores or conjugated double bonds between carbon and oxygen atoms, carbon and nitrogen atoms, carbon and other heteroatoms, and/or carbon and other carbon atoms.
  • fluorophore' refers to a functional group in a molecule which will absorb energy of a specific wavelength and re-emit energy at a different (but equally specific) wavelength. The amount and wavelength of the emitted energy depend on both the fluorophore and the chemical environment of the fluorophore.
  • the photoluminescent carbogenic nanoparticles prepared in accordance with the present invention generally demonstrate higher quantum yields in comparison to photoluminescent surface passivated carbon nanoparticles prepared by prior art methods.
  • the photoluminescence is in the UV-visible spectrum.
  • the quantum yields of the photoluminescent surface passivated carbon nanoparticles prepared in accordance with the present invention may be greater than 15%.
  • Some photoluminescent carbogenic nanoparticles, in particular nitrogen enriched- carbogenic nanoparticles, prepared in accordance with the present invention are photoluminescent under excitation by near infrared frequencies. Photoluminescence may be induced by a two-photon absorption process.
  • a dispersion of solid carbogenic nanoparticles in silane demonstrates photoluminescence with emissions in the range of 400-600 nm when excited at 360 nm.
  • the inventors have therefore concluded that in some embodiments, the carbogenic nanoparticles of the present invention are photoluminescent in the solid state.
  • the carbogenic nanoparticles of the present invention may be prepared from a carbogenic precursor material.
  • 'carbogenic precursor material refers to any suitable organic compound or an organic material which may be carbonised to a carbogenic material at elevated temperatures or with a carbonizing agent.
  • suitable organic materials include, but are not limited to, biomass.
  • the biomass may be sourced from leaf vegetation.
  • suitable organic compounds for use as the carbon precursor substance include, but are not limited to, carbohydrates such as monosaccharides, disaccharides, oligosaccharides, and polysaccharides; polyhydroxy-substituted aldehydes; polyhydroxy-substituted ketones; polyols; heterocyclic compounds including heterocyclic bases and heterocyclic acids; mono- and polyunsaturated hydrocarbons; and heteroatom-substituted oligomers or polymers of ethylene oxide such as PEG 1500N -
  • the term 'carbohydrate ' generally refers to aldehyde or ketone compounds substituted with multiple hydroxy! groups, of the general formula (CH .0 ⁇ ⁇ . wherein n is 2-36, as well as their oligomers and polymers.
  • the carbohydrates of the present invention can in addition, be substituted or deoxygenated at one or more positions.
  • Carbohydrates, as used herein, encompass unmodified carbohydrates, carbohydrate derivatives, substituted carbohydrates, and modified carbohydrates.
  • the phrases "carbohydrate derivatives", " substituted carbohydrate”, and “modified carbohydrates” are synonymous. Modified carbohydrate means any carbohydrate wherein at ieast one atom has been added, removed, substituted, or combinations thereof.
  • carbohydrate derivatives or substituted carbohydrates include substituted and unsubstituted monosaccharides, disaccharides, oligosaccharides, and polysaccharides.
  • the carbohydrate derivatives or substituted carbohydrates optionally can be deoxygenated at any corresponding C-position, and/or substituted with one or more moieties such as hydrogen, halogen, haloaikyL carboxyl, acyl, acyloxy, amino, amido, carboxyl derivatives, aikylamino, dia!kySamino, arylamino, aikoxy, aryioxy, nitres, cyano, suifo, mercapto.
  • Non-limiting examples of suitable carbohydrates which may be used as the carbon precursor substance herein include glucose, fructose, galactose, xylose, ribose, sucrose, iaculose, lactose, maltose, trehalose, celiobiose, raffinose, melezitose, maitotriose, acarbose, sachyose, fructooligosaccharides. galactoo!igosaccharides, mannon-oligosaccharides, cyciodextrin. cellulose.
  • a heterocyclic compound is a cyclic compound which has atoms of at Ieast two different elements as members of its ring(s).
  • the heterocyclic compounds used in the present invention contains at least one carbon atom, and one or more atoms of elements other than carbon with the ring structure, such as sulfuret, oxygen or nitrogen.
  • Heterocyclic bases are organic compounds comprising an aromatic ring in which a lone pair of electrons of a ring-heteroatom (e.g. N, B, S, F, O, P, Si and so forth) is not part of the aromatic system and extends in the plane of the ring.
  • the heterocyclic bases of the present invention can in addition, be substituted at one or more positions or fused with one or more aromatic rings.
  • the heterocyclic bases optionally can be substituted with one or more moieties such as hydrogen, halogen, haloaikyi, carboxyl, acyl, acyloxy, amino, amido, carboxyl derivatives, aikylamino, dialkyiamino, arylamino, aikoxy, aryioxy, nitro, cyano, su!fo, mercapto, imino, suifonyi, suifenyl, sulfinyl, sulfamoyi, carboaikoxy, carboxamido, phosphonyl, phosphinyl, phosphory, phosphino, thioester, thioether, oximino, hydrazine, carbamyl, phospho, phosphonato, boro, si!yi, or any other viable functional group.
  • moieties such as hydrogen, halogen, haloaikyi, carboxyl, acy
  • Non-limiting examples of heterocyclic bases which may be used as the carbon precursor substance herein include pyridine, acricline, pyrazine, quinoxaiine, quinoiine, isoquinoiine, pyrazoie, indazoie, pyrimidine, quinazoiine, pyridazine, cirmoline, triazine, meiamine, and derivatives and combinations thereof.
  • Heterocyclic acids used in the present invention are organic compounds comprising an aromatic ring in which a ring heteroatom may be part of the aromatic ring system and which has an acidic functional group directly or indirectly coupled to the aromatic ring system.
  • hydroxyl groups directly coupled to the aromatic ring by virtue of substitution of the C-ring atoms have acidic functionality.
  • the hetorocyclic acids of the present invention can in addition, be substituted at one or more positions or fused with one or more aromatic rings.
  • the heterocyclic acids optionally can be substituted with one or more moieties such as hydrogen, halogen, haioalkyi, carboxyi, acy!, acyioxy, amino, amido, carboxyi derivatives, aikylarnino.
  • heterocyclic acids which may be used as the carbon precursor substance herein include cyanuric acid.
  • the mono- and unsaturated hydrocarbons of the present invention can in addition, be substituted at one or more positions with one or more moieties such as alkyl, halogen, haioalkyi, carboxyi acyl, acyioxy, amino, amido, carboxyi derivatives, alky!amino, diaikylamirso, arylamino, alkoxy, aryioxy, nitro, cyano, suifo.
  • the carbon precursor substance is glycerine. In another specific embodiment of the invention the carbon precursor substance is melamine. In another specific embodiment of the invention the carbon precursor substance is PEG 1500N - In another specific embodiment of the invention the carbon precursor substance is cyanuric acid. In another specific embodiment of the invention, the carbogenic precursor material is 1 -octadecene.
  • the carbogenic nanoparticles of the present invention may be prepared by carbonizing a carbogenic precursor material in a high boiling point solvent.
  • carbonizing refers to a process which reduces or converts a carbon-containing substance, such as any one of the suitable organic compounds referred to above, to a carbon-based material.
  • the carbonizing process may include any one or more sequential depolymerisation, decomposition, dehydration including intramolecular dehydration, polymerisation and pyrolysis processes.
  • carbonizing the carbogenic precursor material in the high boiling point solvent comprises bringing the carbogenic precursor material in contact with the high boiling point solvent at an elevated temperature.
  • carbonizing the carbogenic precursor material in the high boiling point solvent comprises heating a mixture or solution of the carbogenic precursor material in the high boiling point solvent to the elevated temperature and maintaining said mixture or solution at the elevated temperature.
  • the elevated temperature will be at or above a temperature at which the carbogenic precursor material will thermally decompose to a carbon-based material. Accordingly, in some embodiments the elevated temperature may be in a range of about 100 °C to about 300 °C.
  • the high boiling point solvent is a solvent that has a boiling point temperature that is greater than the temperature at which the carbogenic precursor material may thermally decompose to the carbon-based material.
  • Suitable high boiling point solvents include, but are not limited to, ionic liquids, glycerine, long chain unsaturated hydrocarbons such as 1-octadecene, and long chain saturated hydrocarbons.
  • the high boiling point solvent has a boiling point temperature greater than 250 °C.
  • carbonizing the carbogenic precursor material may also comprise treating the carbogenic precursor material with a carbonizing agent.
  • the carbogenic nanoparticles of the present invention may also be prepared by carbonizing a carbogenic precursor material in a high boiling point solvent in the presence of an acid.
  • the acid may be an inorganic acid or an organic acid.
  • Suitable inorganic acids include, but are not limited to, sulphuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, boric acid, hydrobromic acid, fluorosulphuric acid, and hexafluorophosphoric acid.
  • Acid-enriched solid zeolite catalysts such as ZSM-5 zeolite, are also suitable.
  • Suitable organic acids include but are not limited to organic acids such as monofunctional or polyfunctional carboxylic acids and/or anhydrides, in particular polyhydroxy-substituted carboxylic acids and/or anhydrides; sulphonic acids;
  • Monofunctional carboxylic acids as used herein are organic acids comprising a carboxylic acid group and optionally one or more functional groups, including functionalised and non-functionalised carboxylic acids.
  • Monofunctional carboxylic acids useful herein can be aliphatic, aromatic, saturated, linear and/or branched.
  • the preferred monofunctiona! carboxylic acids have from about four to about twenty-four carbon atoms.
  • the functionalisecl monofunctional carboxylic acids can be substituted with one or more moieties such as hydrogen, halogen, haloalkyl, carboxyl, acyl, acyloxy, amino, amiclo, carboxyl derivatives, alkylamino, dialkylamino, arylamino, a koxy, aryloxy, nitro, cyano, sulfo, mercapto, imino, sulfonyl, suifenyl, sulfinyl, sulfamoyi, carboalkoxy, carboxamido, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, oximino, hydrazine, carbamyi, phospho, phosphonato, boro, si!yi, or any other viable functional group.
  • moieties such as hydrogen, halogen, haloalkyl, carboxyl,
  • Non-limiting examples of suitable monofunctiona! carboxy!ic acids which may be used as the carbon precursor substance herein include isohutyric acid, benzoic acid, 2-ethyl butyric acid, hexanoic acid, heptanoic acid, 2 ⁇ ethyihexanoic acid, octanoic acid, nonanoic acid, 3,5,5-trimethyihexanoic acid, isononanoic acid, decanoic acid, isooctadecanoic acid, dodecanoic acid, 2-methyl butyric acid, isopentanoic acid, pentanoic acid, 2-methyl pentanoic acid, 2-methyl hexanoic acid, isooctanoic acid, undecyiinic acid, isolauric acid, isopaimitic acid, isosiearic acid, behenic acid, and derivatives and combinations thereof.
  • the polyfunctions! carboxy!ic acid is a oarboxyiic acid with at least two carboxyiic acid groups and optionally one or more additional functional groups, including functionaiized and non ⁇ functionaiized dicarboxyiic acids.
  • Polyfu notional carboxyiic acids and/or anhydrides can be aliphatic, aromatic, saturated, linear and/or branched.
  • the polyfunctionai carboxyiic acids and/or anhydrides used herein have one to about thirty six carbon atoms.
  • the functionalised polyfunctionai oarboxyiic acids can be substituted with one or more moieties such as hydrogen, halogen, ha!oaikyi, carboxyl, acyl, acy!oxy, amino, amido, carboxyl derivatives, alkyiamino, diaikyiamino, ary!amino, aikoxy, ary!oxy, nitro.
  • moieties such as hydrogen, halogen, ha!oaikyi, carboxyl, acyl, acy!oxy, amino, amido, carboxyl derivatives, alkyiamino, diaikyiamino, ary!amino, aikoxy, ary!oxy, nitro.
  • Non-limiting examples of polyfunctionai carboxyiic acids and/or anhydrides which may be used as the organic acid herein include carbonic acid, hexanedioie acid, dimer acid, azelaic acid, sebacic acid, dodecanedioic acid, glutaric acid, succinic acid, citric acid, phtha!ic acid, isophthaiic acid, terephthalic acid, 2,6-naphthalene dicarboxyiic acid, and derivatives and combinations thereof.
  • the inventors speculate that the role of the acid is to initiate, catalyze or facilitate conversion of the precursor carbogenic substance to carbogenic nanoparticles at elevated temperatures.
  • the acid may be involved in several acid- catalysed reactions, such as amine-alkylization, which may increase the number of fluorophores in the core or surface of the carbogenic material of the nanoparticle, thereby enhancing the quantum yield of the carbon nanoparticles prepared by the methods of the present invention.
  • the inventors have found that photoluminescent carbogenic nanoparticles may be prepared in a similar manner as described above by carbonizing a carbogenic precursor material, optionally with an acid, in a high boiling point solvent in the presence of a surface passivating agent. Additionally, while some carbon nanoparticles prepared in accordance with the present invention may display inherent photoluminescence properties, their quantum yield may be enhanced by preparing said carbon nanoparticles in the presence of a surface passivating agent.
  • the surface passivating agent may be any suitable organic compound capable of binding to a surface of the carbogenic nanoparticles by primary or secondary bonding interactions, such as for example, through amidation, hydrogen bonding, or electrostatic attraction forces or adsorption.
  • Suitable examples of surface passivating agents include, but are not limited to, long chain amines, amphiphilic oligomeric polymers, long-chain surfactants, nucleotides, peptides, and so forth.
  • the passivating agent may be 1 -hexadecylamine, PEG1500, and organo-silanes such as triethylsilane.
  • the surface passivating agent is soluble in the high boiling point solvent.
  • concentration of the surface passivating agent in the high boiling point solvent may be about 0.01 wt% to about 50 wt%.
  • the carbogenic nanoparticles of the present invention may be prepared in accordance with the present invention and subsequently treated with a surface passivating agent by methods well understood in the art to produce surface passivated carbogenic nanoparticles.
  • carbogenic nanoparticles may be particularly suitable where the surface passivating agent is an inorganic compound or a metal.
  • Suitable inorganic compounds which may be surface passivating agents include, but are not limited to, CdS, ZnS.
  • Suitable metals which may be surface passivating agents include, but are not limited to, Au, Ag, Zn.
  • the carbogenic nanoparticles may be bonded to surface passivating agents which are metals by reacting the carbogenic nanoparticle with a metal precursor compound and subsequently converting the metal precursor compound to the metal.
  • One such example includes reacting the carbogenic nanoparticles with silver nitride and subsequently reducing silver nitride to silver metal to prepare carbogenic nanoparticles surface passivated by silver metal.
  • the carbogenic precursor material may be in a solid or liquid phase or a gel form. It may be brought into contact with the high boiling point solvent by dispersing the carbogenic precursor material in the high boiling point solvent.
  • dispersing the carbogenic precursor material in the high boiling point solvent may be achieved by stirring a mixture of the carbogenic precursor material and the high boiling point solvent with a mixer or agitator.
  • dispersing the carbogenic precursor material in the high boiling point solvent may be achieved by rapidly stirring a mixture of the carbogenic precursor material and the high boiling point solvent with a mixer or agitator.
  • the acid may already be present in the high boiling point solvent, or the acid may be dispersed in the high boiling point solvent, as has been described above with respect to the carbogenic precursor material.
  • the acid may be added to the high boiling point solvent in a liquid or a solid form.
  • the carbogenic precursor material may be the high boiling point solvent itself and thus already be in the liquid phase.
  • the acid may be brought into contact with the high boiling point solvent (i.e. the carbogenic precursor material) by dispersing the acid in the high boiling point solvent, as has been described above with respect to the carbogenic precursor material.
  • the acid may be added to the high boiling point solvent in a liquid or a solid form.
  • the temperature of the high boiling point solvent may already be elevated to the desired elevated temperature when the carbogenic precursor material and/or the acid (if required) and/or surface passivating agent (if required) is added to the high boiling point solvent.
  • a mixture or solution of the carbogenic precursor material and/or the acid (if required) and/or the surface passivating agent (if required) may be provided and then the mixture or solution may be heated to the desired elevated temperature and maintained at that temperature until the reaction is completed.
  • the invention may be readily adapted to a form of continuous processing. Suitable examples of continuous processing include, but are not limited to, spinning disc processing, tubular reactor processing, and rotating tubular reactor processing.
  • the method of the present invention may be performed in a period up to 24 hours, preferably in a period up to about 180 minutes. It will be appreciated that reactions performed at lower temperatures of under 150 °C are likely to proceed to completion in periods of 12 -24 hours, whereas reaction performed at higher temperatures are likely to proceed to completion in periods of 180 minutes or less.
  • carbogenic nanoparticles including photoluminescent carbogenic nanoparticles
  • concentration of concentrated sulfuric acid 98%
  • Concentrated sulfuric acid 98% is a known carbonizing agent.
  • the final products were purified by precipitating with acetone three times.
  • the as- obtained photoluminescent carbon nanoparticles were highly soluble in common non- polar organic solvents, such as hexane, chloroform, and toluene.
  • non-surface passivated carbon nanoparticles were also synthesized in the absence of a surface passivating agent (ie. 1 -hexadecylamine) with all other reaction conditions identical.
  • a surface passivating agent ie. 1 -hexadecylamine
  • Mw cellulose ester membrane bag
  • TEM measurements were performed on Philips Tecnai F20 at operating voltage of 200 kV.
  • AFM Imaging were obtained by dropping diluted solutions of bare CDs, OCDs and WCDs onto freshly cleaved mica surface and dried in air. All samples were imaged in air by tapping mode AFM on a Dimension 3100 with OMCLAC 160 tip (TS-W2, silicon).
  • Fourier-transform infrared spectra of the purified samples were recorded on a Nicolet 730 FT-IR spectrometer. UV Vis spectra were recorded at room temperature on a Perkin-Elmer Lambda 9 spectrophotometer.
  • PL spectra were measured on a J&M Fluoreszenzspektrometer 3095SL.
  • both the OCDs and WCDs can only be excited in a short range of excitation wavelengths ( Figure 1 B and Figure 2A), however, when the reactions were left to proceed to 3h, the excitable range broadened significantly into the longer wavelength with much enhanced emission intensity in the longer wavelength spectrum ( Figure 1 C and Figure 2B). This phenomenon is particularly pronounced in the case of the OCDs, where the upper end of the excitable wavelength increased from 480nm to 560 nm.
  • the morphology of the OCDs extracted at 5min and 180min were characterized by high-resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM).
  • HRTEM transmission electron microscopy
  • AFM atomic force microscopy
  • the OCDs are highly mono- disperse and are mostly spherical dots with diameters in the range of 4-7 nm without noticeable difference.
  • the WCDs have similar size and morphology in comparison with the OCDs. This leads to our speculation that it was not the size change that has altered the QY of the OCDs over the reaction time, whereas it may be the OCD particle surface that has continuously evolved, which may have resulted in the changes in emissive sites, hence the QYs.
  • N-WCD water soluble photoluminescent nitrogen-enriched carbogenic nanoparticles
  • Example 6 Synthesis of photoluminescent carbogenic nanoparticles from biomass
  • 1 -octadecene 15 ml was placed into a 100 mL three-necked flask and degassed with Argon for 10 min.
  • the solution temperature was increased to 300°C.
  • Dried tree leaves (no specification) ground into small pieces was added into the flask.
  • the temperature was maintained at 300°C for up to 3 hours and then allowed to cool to ambient temperature unassisted.
  • the product was photoluminescent with a quantum yield of the water-suspended fluorescent species at excitation 360 nm 6 - 7 %.
  • the mixture was purified by dialyzing against Milli-Q water with MWCO (molecular weight cut-off) 3500 dialysis tubing (SpectroPor 6). It was found that part of the sample could easily penetrate the tubing of MWCO3500.
  • the fraction passing through the MSCO 3500 dialysis tube was further separated by MWCO 1000 dialysis tubing and column chromatograph.
  • the three fractions obtained, which were dialyzed by MWCO 3500, MWCO 1000 dialysis tubing, and column chromatography, are labeled as 3.5K, 1 K, and ⁇ 1 K, respectively.
  • the particle size of each fraction was determined by fluorescence correlation spectra as indicated in the table below.
  • Figure 1 1 The spectra of UV-visible absorption, photoluminescence, and excitation the three fractions are presented in Figure 1 1 .
  • Figures 1 1 (b)-(d) shows the photoluminescence spectra of ⁇ 1 K, 1 K, and 3.5K fractions under excitation from 330 nm to 450 nm, respectively. They are all multicolored and the emission maxima shift bathochromically as the excitation wavelength increases from 32 nm to 600 nm.
  • the emission intensity of the ⁇ 1 K fraction is higher than the 1 K fraction, which is higher again than the 3.5K fraction.
  • the quantum yields, which were calibrated against quinine sulphate, were 22.4 %, 10.2 % and 5.4% for the ⁇ 1 K, 1 K, and 3.5K fractions, respectively.
  • FTIR Fourier transform infrared spectra
  • Glycerine (10 ml) was added to a 250 ml three neck round bottom flask and heated to 280 °C under nitrogen.
  • One drop of concentrated sulfuric acid (98%) was added into the flask and the mixture was refluxed for 15 minutes, followed by cooling to ambient temperature.
  • Example 10 Synthesis of photoluminescent carbogenic nanoparticles at room temperature a) Cyanuric acid (0.5 g) was mixed with glycerine (10 ml) with stirring at room temperature. Concentrated sulfuric acid (10 ml, 98%) was added to the mixture. b) Melamine (0.5 g) was mixed with glycerine (10 ml) with stirring at room temperature. Concentrated sulfuric acid (10 ml, 98%) was added to the mixture.
  • Citric acid 0.5 g was mixed with glycerine (10 ml) with stirring at room temperature. Concentrated sulfuric acid (10 ml, 98%) was added to the mixtures.

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Abstract

La présente invention concerne un procédé de préparation de nanoparticules à base de carbogène. Ledit procédé comprend une étape de saturation d'un matériau précurseur à base de carbogène, de préférence par traitement à haute température de celui-ci au moyen d'un acide dans un solvant présentant un point d'ébullition élevé. Le rendement quantique de certaines desdites nanoparticules à base de carbogène est supérieur à environ 15 %. La photoluminescence desdites nanoparticules à base de carbogène peut être encore renforcée par traitement du matériau précurseur à base de carbogène au moyen d'un acide dans un solvant présentant un point d'ébullition élevé en présence d'un agent de passivation de surface.
PCT/AU2011/000998 2010-08-05 2011-08-05 Procédés de préparation de nanoparticules à base de carbogène et nanoparticules photoluminescentes à base de carbogène Ceased WO2012016296A1 (fr)

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