CN101600646A - The nanostructured composites of nanotube and carbon-coating - Google Patents

The nanostructured composites of nanotube and carbon-coating Download PDF

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CN101600646A
CN101600646A CNA200780051101XA CN200780051101A CN101600646A CN 101600646 A CN101600646 A CN 101600646A CN A200780051101X A CNA200780051101X A CN A200780051101XA CN 200780051101 A CN200780051101 A CN 200780051101A CN 101600646 A CN101600646 A CN 101600646A
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carbon
nanotube
cnt
coating
substrate
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戈登·乔治·***
陈俊
安德鲁·伊恩·米内特
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University of Wollongong
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Abstract

The present invention relates to nanostructured composites, described nanostructured composites comprises the nanotube network that is partially submerged into carbon-coating at least.The present invention be more particularly directed to the nanostructured composites of conduction is used for power conversion, energy field of storage and biomedical sector.The invention still further relates to a kind of chemical vapour deposition technique that passes through, carbon is deposited to the method that is positioned on the suprabasil catalyst layer.

Description

The nanostructured composites of nanotube and carbon-coating
Technical field
The present invention relates to nanostructured composites, in particular for the electrical-conductive nanometer structural composites of power conversion, energy storage and biomedical sector.The invention still further relates to a kind of method for preparing described nanostructured composites.
Background technology
Along with the minimizing of non-renewable fuel energy, the utmost point needs more effective power conversion and storage means.Common energy storage device such as battery and capacitor rely on electrode to come work.
The electrode of photochemical cell requires surface area big, so that the electric charge effective mobility is in electrolyte.Electrode in the charge storage device therefor also requires the big and conductance height of surface area.
Bioelectrode is used for to the organism delivered charge of living, or is used in the organism that lives or perception electric pulse on the organism that lives.Common bioelectrode comprises pacemaker electrode and electrocardiogram (ECG) electronic pads.Interaction between the organism of electrode and work is very important for long-term use.Electrode must be a biocompatibility, so that this electrode pair is implanted the organism of work of this electrode is nontoxic.
The implantable bio-electro utmost point that is used for human body that is purchased is made by platinum and platinum-iridium alloy.These metals are usually with titanium nitride or conductive oxide (RuO for example 2Or IrO 2) carry out coated with increasing its surface area or regulating their biological interaction.
Nanotube, CNT for example is for the electrode of making electrochemical apparatus provides new material.These electrodes require conductance height, intensity height and surface area big.The two kinds of requirements in back can not be satisfied usually simultaneously.The electrode that is made of CNT (Bark paper, bucky paper) has high surface area fully, but is not durable usually, not pliable and tough, does not have the required sufficiently high conductance of actual macroscopic view application.
The research of a lot of manufacturing CNTs has been arranged, for example, constructed the CNT platform by forming the aligned carbon nanotube array.People such as Li 1Reported first vertical orientated CNT extensive synthetic, they have put down in writing and have utilized based on the synthetic on a large scale aligned carbon nanotube of the chemical vapour deposition technique that embeds the Fe nanometer particles catalysis in the mesoporous silicon oxide.
Be printed with the manufacturing technology of making aligned carbon nanotube bunch (forests) and array on the planar substrates of catalyst by chemical vapour deposition (CVD), usually need in independent procedure of processing, be the form of nano particle assembly or film with catalyst material deposition and Butut.This makes the manufacture method of nanotube become complicated 2,3
In addition, up to now, require in nonconducting substrate, to carry out the growth of carbon nano tube bundle and/or other type nanometer tube bundle.Therefore, need be with the substrate of bunch transferring to conduction of these orientations 4, perhaps before being suitable for use as the electrode material of the equipment of being integrated into, on described bunch, metal is deposited the contact 5Carry out post processing.
Usually, chemical gaseous phase depositing process generates the nanotube be not connected with substrate, and they are open and flat in substrate, therefore with any connection of substrate all do not have mechanical strength or electricity intensity (robust).
Need a kind of simple method for preparing nanostructured composites of research.These nanostructured composites need have mechanical strength and preferably have sufficiently high conductance, to be used for such as the energy storage and to change with application such as electrodes.
Summary of the invention
The invention provides a kind of nanostructured composites, it comprises the nanotube network that is incorporated into carbon-coating.
" be incorporated into " to refer at least and be partially submerged in the carbon-coating.
In one embodiment, described compound conducts electricity.Preferred described carbon-coating is a high conductivity, such as activated carbon layer (CL), and amorphous carbon (AC) layer for example.This embodiment is particularly useful to power conversion and storage.
Nanostructured composites also can comprise substrate, and therefore the nanostructured composite basal structure is provided.
Preferably, described carbon-coating is connected with described substrate." connection " refers to by physical action and is retained in the substrate.
Therefore in one embodiment, substrate is a metal, has produced the nanostructured composite basal structure with conduction property as the metal.
In one embodiment, compound is a biocompatibility, has therefore produced biomaterial composites.Nanotube and/or carbon-coating can be biocompatibilities.Comprise also when compound under the situation of substrate that nanotube, carbon-coating and/or substrate can be biocompatible.
The present invention further provides a kind of method that is used to prepare nanostructured composites or nanostructured composite basal structure, said method comprising the steps of:
I) metallic catalyst is deposited in the substrate;
Ii) by chemical vapor deposition (CVD), the nanotube network that has carbon-coating below making grows out from described suprabasil catalyst, forms the nanostructured composite basal structure; And
Iii) randomly, separate described nanostructured composites from described substrate.
Nanotube is orientated, so that they stretch out from described carbon-coating in nanostructured composites.Nanotube partly embeds carbon-coating, that is, with the initial growth point embedding carbon-coating of nanotube, and the remainder of nanotube stretches out from carbon-coating.In other words, nanotube grows out from metal nanoparticle, forms the tight connection between nanotube and the carbon-coating thus, and wherein said metal nanoparticle is to form by the organo-metallic catalyst reduction that will embed in the carbon-coating.
In one embodiment, step I i) substrate is the form of decentralized medium, randomly, comprises biomolecule, and described decentralized medium is cast on the nanotube layer.
The present invention further provides a kind of goods, described goods are made of above-mentioned nanostructured composites and/or all or part of of nanostructured composite basal structure.Preferably, described goods conduct electricity, and example comprises the electrode that is used for as capacitor, hybrid battery capacitor, ultracapacitor and storage of battery homenergic and conversion; Electrode as fuel cell, atmosphere storage medium and sensor; Be used for as bioelectrode the electrode of the biomedical sectors such as substrate of biological fuel cell and electro photoluminescence biological growth.
Nanostructured composites
Usually compound is described as the material made by two or more composition materials, described composition material keeps separating in the structure of making and independence.Usually, composition material is two classes, generally is described to matrix material and reinforcement material.It has been generally acknowledged that matrix material surrounds and the bracing reinforcement material, reach a kind of synergy, have enhanced propertied material thereby produce.
In the present invention, provide nanostructured composites, wherein, regard nanotube as matrix material, and the carbon-coating that will be connected with them has been regarded the reinforcing to compound as.For example, compare with the electrode that is made of CNT (Bark paper) fully, this arrangement provides intensity bigger material.
The small cylinder that nanotube is normally made by the organic or inorganic material.The known type of nanotube comprises CNT, inorganic nano-tube and peptide nanotube (peptidyl nanotubes).Inorganic nano-tube comprises WS 2And metal oxide nanotubes (as titanium oxide and molybdenum oxide nanotube).Preferred nanotube is CNT (CNT).
CNT is the graphite flake that is rolled into cylindrical tubes.The basic repetitive of graphite flake is made of the hexatomic ring of carbon atom, and carbon-carbon bond is about
Figure A20078005110100081
According to their constituted mode, nanotube can be single-walled nanotube (SWNT), double-walled carbon nano-tube (DWNT) and/or many walls nanotube (MWNT).Common SWNT diameter is about 0.7-1.4nm.
The architectural feature of nanotube provides unique physical property for them.
The mechanical strength of nanotube can reach 100 times of steel mechanical strength, and length can reach several millimeters.According to the chirality degree or the degreeof tortuosity of nanotube, they show metal or semi-conductive electrical characteristic.The multi-form of known nanotube is armchair (armchair), sawtooth pattern (zigzag) and chiral nanotubes.The electrical properties of CNT is partly also determined according to " form " of nanotube thus by the diameter of nanotube.
Local irregularities and core (central core) that space between the CNT graphite linings, defect sturcture produce should allow bigger embedding ability.Stability is high, mass density is low, resistance is low because they have, accessible surface is greatly long-pending and pore-size distribution is narrower, so CNT is the appropriate materials of electrochemical capacitor.
Nanotube is orientated, so that they stretch out from carbon-coating in compound of the present invention.Nanotube is partly embedded in the carbon-coating, that is, the part of nanotube one end is embedded in the carbon-coating, and the remainder of nanotube stretches out from carbon-coating.In other words, nanotube grows out from metal nanoparticle, thereby forms the tight connection between nanotube and the carbon-coating, and described metal nanoparticle forms by the organo-metallic catalyst reduction that will embed in the carbon-coating.Prepare nano-complex by relate to the method that metallic catalyst deposits in substrate.In the method, make the metal nanoparticle of catalyst embed carbon-coating, we can say that nanotube grows out from these metal nanoparticles, caused the tight connection between nanotube and the carbon-coating.
The nanotube of nano-complex preferably can form the non-orientation nano pipe of three dimensional entanglement network.Nanotube can be single-walled nanotube (SWNT), double-walled nanotubes (DWNT) and/or many walls nanotube (MWNT).Preferred nanotube is many walls nanotube of non-orientation, is normally defined: many walls nanotube network of non-orientation or bunch.
The multi-walled carbon nano-tubes of the preferred non-orientation of nanotube (MWNT), average length are preferably greater than 50 μ m greater than 1 μ m, and more preferably greater than 100 μ m, external diameter is 10-100nm, is preferably 20-40nm.
The orientation CNT be high-sequential and think to have good electrochemical properties.Yet the compound that contains non-orientation nano pipe also demonstrates good electrochemical properties, and is in some cases, better than the vertical orientated nanotube of growing in identical heating furnace.
As mentioned above, nanotube is orientated in nano-complex, they are stretched out from carbon-coating.Described carbon-coating preferably conducts electricity, and in this embodiment, the carbon-coating of conduction means that the plated metal contact on nanotube that can avoid requiring in the past is to obtain conductive material.Nanotube grows out from carbon-coating itself and just makes nanotube be incorporated into carbon-coating.
The preferred activated carbon layer of described carbon-coating (CL), amorphous carbon (AC) layer for example, more preferably non-graphitized carbon-coating.
In one embodiment, the thickness of carbon-coating preferably less than 5 μ m, is more preferably less than 1 μ m less than 10 μ m.SEM imaging (referring to Fig. 1) demonstrates the tight continuous amorphous carbon film of the homogeneous with nano-scale loose structure.It is amorphous carbon irregular but activation that the XRD spectrum demonstrates this amorphous carbon layer.
Carbon-coating can contain the metal that derives from the metallic catalyst that uses in the preparation compound method or the combination of metal.The metal that derives from metallic catalyst can be transition metal such as palladium, iron, rhodium, nickel, molybdenum and/or cobalt, preferred iron, nickel or cobalt.
The tenor of carbon-coating can preferably less than 10%, be more preferably less than 5% (being obtained by the energy dispersion X-ray analysis method) less than 20%.Under such low concentration, think that only tenor is not the reason that makes the carbon-coating conduction.
Preferably, the existing pliability of compound has intensity again.Carbon-coating increases composite strength, has more kept enough big suppleness, thereby has made its moulding to be used for various uses.Compound can have different-thickness.Preferably, composite thickness is 1-100 μ m, more preferably 5-50 μ m, and 20 μ m most preferably from about make it be suitable for pliable and tough thin ultracapacitor and as the anode material as batteries such as Li-ion rechargeable ponds.
Compound can further comprise substrate, and therefore the nanostructured composite basal structure is provided.
Substrate is used to prepare nano-complex of the present invention.This substrate provides the surface, prepares catalyst film on described surface, and is the nanotube network of carbon-coating below described superficial growth goes out.The growth needs high temperature of nanotube is about 500 ℃ and higher usually.Utilization relates to the chemical vapor deposition (CVD) of substrate can finish this step, and described substrate can withstand at inert atmosphere for example Ar or N 2The required high temperature of growing nano-tube in the gas.Substrate can be conduction or nonconducting.
The example of the conductive substrates that is fit to comprises vitreous carbon (glassy carbon); Metal or metal forming, for example metal or their metal formings such as copper, iron, nickel, platinum and aluminium; The quartz plate of washing and glass (glassy slides); Carbon paper such as carbon fiber paper; Carbon; Carbon nano-tube fibre; With CNT paper.
The example of the non-conductive substrate that is fit to comprises for example metal oxide film of quartz, silicon wafer, glass and inorganic composite.
Selectively, nano-complex is to separate and independent the use with the substrate for preparing this compound thereon.In this selectable arrangement, compound can be transferred in another substrate with suitable required application feature.Can from above-named those examples, select substrate, perhaps can from any other substrate, select, not require to be able to take the required high temperature of nanotube growth, as non-cohesive material (for example metal) and polymeric material.
In one embodiment, use metallic substrates to produce to have the compound underlying structure of conduction property as the metal.
The example of the metallic substrates that is fit to comprises platinum, metal forming (Copper Foil and the aluminium foil that is used for capacitor that for example are used for chargeable battery), the film of washing, the textile of washing and the polymer fiber of washing.
Polymeric substrates can comprise poly-(styrene-β-isobutene-β-styrene) (SIBS), described poly-(styrene-β-isobutene-β-styrene) is soft, resilient triblock copolymer, and biological stability and biocompatibility become effective biomaterial preferably because of it.Other polymeric substrates comprises that electric conductor is as poly-enedioxy thiophene (PEDOT), solubility pyrroles, polythiophene and/or polyaniline; Acrylate polymer; Acrylate copolymer; Polyacrylate; Polyacrylamide; Polyacrylonitrile; Chlorinated polymeric; Fluorinated polymer; Styrenic; Polyurethane; Natural rubber; The synthetic rubber polymer; Vinyl chloride-acrylate polymer; And their copolymer.The object lesson of polymeric substrates comprises polyvinyl acetate, poly-(acrylic acid), polymethyl methacrylate, polyacrylamide, polyacrylonitrile, polyvinyl proprionate, polystyrene, polytetrafluoroethylene (PTFE), polyvinyl chloride, poly-inclined to one side 1,1-dichloroethylene, poly-(vinyl chloride-ethylene), poly-(vinyl chloride-propylene), poly-(styrene-butadiene-copolymer), copolymer in cinnamic acrylic ester, ethylene-vinyl chloride copolymer, poly-(vinyl acetate-acrylate), poly-(vinylacetate-ethene) and combination thereof, but be not limited thereto.
In another embodiment, nanotube, carbon-coating and/or substrate for example can be carried out chemical modification by connecting biomolecule, catalyst and/or additional conductors.
When connecting biomolecule, can produce biocompatibility compound and/or underlying structure as biomaterial.
Term " biomolecule " be often referred to the molecule in organism that lives or cell, found or polymer and with the compound of this interaction of molecules.Example comprises biological polyelectrolytes, for example hyaluronic acid (HA), shitosan, heparin, chondroitin sulfate, polyglycolic acid (PGA), PLA (PLA), polyamide, poly--2-hydroxyl-butyrate (PHB), polycaprolactone (PCL), polylactic-co-glycolic acid copolymer (PLGA), protamine sulfate, PAH, polydiene propyl-dimethyl ammonium, polymine, You Teqi polyacrylic resin (eudragit), gelatin, spermidine, albumin, polyacrylic acid, sodium alginate, poly styrene sulfonate, carrageenan, carboxymethyl cellulose; Nucleic acid class, for example DNA, cDNA, RNA, oligonucleotide, oligoribonucleotide, modified oligonucleotide, modified oligoribonucleotide and peptide nucleic acid (PNA) or its hybrid molecule; Polyaminoacid, for example poly-L-Lysine, poly--the L-arginine, poly--the L-aspartic acid, poly--D-glutamic acid, poly--L-glutamic acid, poly-L-histidine and poly-(DL)-lactide; Protide, for example growth factor receptors, catecholamine acceptor, amino acid derivativges acceptor, cytokine receptor, lectin, cell factor and transcription factor; Enzyme, for example protease, kinases, phosphatase, GTP enzyme and hydrolase; Polysaccharide, for example cellulose, amylose and glycogen; Lipid, for example chylomicron and glycolipid; And steroids, for example amino hormone, peptide hormone and steroid hormone of deriving.
Polyelectrolyte is to have can the dissociate polymer of group of ion, can be the component or the substituent of polymer chain.Usually, to such an extent as in the polyelectrolyte these ions can dissociate the polymer (being also referred to as polyion) of the very big dissociated state of quantity of group for water dissolvable.According to the type that can dissociate group, polyelectrolyte is divided into polyacid and polyacid base usually.When dissociating, along with proton separates, polyacid forms polyanion, and polyacid can be inorganic polymer, organic polymer and biopolymer.Polyacid base contains the group that can accept proton (for example by forming salt with acid reaction).
The structure of some biomolecule that is suitable for compound of the present invention and compound underlying structure is as follows:
Figure A20078005110100121
Shitosan
Figure A20078005110100122
Glucuronic acid N-acetyl group-aminoglucose
Hyaluronic acid (b)
Figure A20078005110100123
Chondroitin sulfate
Figure A20078005110100124
Heparin
Be understandable that biomolecule can comprise the functional group that allows further to control biological interaction, as transports active component for example medicine, steroids, growth factor or antibiotic biomolecule.Also can be according to required application choice biomolecule, for example, if compound will be used to promote or suppress the adhesion of specific cell type, it may be favourable then utilizing the biomolecule that promotes nerve cell or endothelial cell growth or suppress smooth muscle cell growth (fibroblast).
Biomolecule can comprise monomer (for example pyrroles) and/or oxidant (FeCl for example 3).In this embodiment, biomolecule can be conducted electricity,, can realize conduction,, then realize conduction by gas-phase polymerization if perhaps have more than one oxidant in the substrate by subsequently electrochemistry or chemical oxidation if there is more than one monomer in the substrate.
Can there be a plurality of biomolecule in nano-complex of the present invention and/or the substrate.Determine the selection of biomolecule according to the final use of compound or compound underlying structure.
Also can utilize additional conductors such as metal to come the decorated nanometer tube-surface, or utilize conducting polymer to come the decorated nanometer tube-surface by solution chemistry polymerization or gas-phase polymerization or electro-deposition by sputter coating or electro-deposition.
Method
The method that is used to prepare nanostructured composites or nanostructured composite basal structure may further comprise the steps:
I) metallic catalyst is deposited in the substrate;
Ii) by chemical vapor deposition (CVD), the nanotube network that has carbon-coating below making grows out from described suprabasil catalyst, forms the nanostructured composite basal structure; And
Iii) randomly, separate described nanostructured composites from described substrate.
The first step relates to the metallic catalyst film is deposited in the substrate.Substrate provides the surface, prepares catalyst film on described surface, grow nanotube from described surface catalyst film, and form carbon-coating on described surface.
Catalyst can be any catalyst that is fit to the growth of catalytic nanometer pipe.
Metallic catalyst can be organo-metallic catalyst or inorganic metal catalyst, preferred organic metal salt catalyst.
Organo-metallic catalyst comprises the metal-carbon key.The carbon of this metal-carbon key be nucleophilicity and also can produce carbon-carbon bond.There is hypothesis to think that this has started the growth of nanotube, especially CNT.
The metal of metallic catalyst can be transition metal such as palladium, iron, rhodium, nickel, molybdenum and cobalt, preferred iron, nickel or cobalt.
The organic salt that is fit to comprises the aryl or the heteroaryl sulfonate of any replacement, for example, and toluene fulfonate, alkylbenzenesulfonate and pyridine-sulfonic acid salt; And carboxylate acetate for example, or acetylacetonate.
The object lesson of organic metal salt catalyst is as follows:
P-methyl benzenesulfonic acid iron (III) (Fe (III) pTS)
Figure A20078005110100141
DBSA iron (III) (Fe (III) DBS)
Figure A20078005110100142
Pyridine-sulfonic acid iron (III) (Fe (III) PS)
Figure A20078005110100143
Camphorsulfonic acid iron (III);
Nickel acetate (II);
Nickel acetylacetonate (II);
Cobalt acetate (II); With
Acetylacetone cobalt (II).
Can prepare catalyst film in the substrate by making slaine and organic compound be dissolved in solvent and it being deposited on.For example, can be by making FeCl 3With NaCSA be to be mixed in preparation catalyst film in the organic solvent (for example ethanol) at 1: 1 with mol ratio.Selectively, catalyst can directly deposit in the substrate from organic solvent (for example ethanol).Can carry out removing organic solvent by annealing before second step then.
Can use any suitable known technology such as spin-coating method to make the catalyst film deposition.Preferred catalyst forms stable film in substrate.This film can have the suitable depth of catalytic nanometer pipe growth.Preferred catalyst film thickness＜50 μ m, more preferably＜10 μ m.
Use different catalysts can influence nanotube growth, cause various nanotube length and diameter.Selection of catalysts also can influence the porosity of nanotube.For example, Fig. 7 demonstrates when with when those CNTs of Fe (III) PS (referring to Fig. 7 b) and Fe (III) pTS (referring to Fig. 7 c) growth are compared, from Fe (III) DBS (referring to Fig. 7 a) carbon nanotubes grown be to have short larger-diameter nanotube.D DBS＞D PS＞D PTS(D=diameter) and L DBS＜L PS＜L PTSThe trend of (L=length) is attributable to the heterogeneity of Fe (III) organic moiety.
The CNT that quality is the highest, it is the carbon nano tube bundle with maximum pore rate, grows out from metallic catalyst Fe (III) pTS.
Selection of catalysts also influences the square resistance of gained nano-complex carbon-coating.For example, find that square resistance is respectively every square 46 Ω, 86 Ω, 65 Ω and 57 Ω for Fe (III) pTS, Fe (III) DBS, Fe (III) PS and Fe (III) CSA.Therefore, Fe (III) pTS becomes most preferred catalyst because of it produces the highest compound of electric conductivity.
Second step of preparation nano-complex relates to by chemical vapor deposition (CVD), and the nanotube network that has carbon-coating below making grows out from suprabasil catalyst film.In this step, use carbon source, preferred gaseous carbon source.Have been noted that: when not having carbon source, find the about 5k Ω of resistance of carbon-coating.Add carbon source in growth step, it is original more than 1/100 that carbon-coating resistance is reduced to, thereby it is more conducted electricity.
The example of carbon source comprises alkane, alkene, alkynes and/or aryl and its derivative.The example of the alkane that is fit to is methane, ethane, propane, different propane, butane, iso-butane, secondary butane, uncle's butane, pentane, neopentane, hexane etc.The example of the alkene that is fit to is ethene, propylene, 1-butylene, 2-butylene, 2-metering system, 3,3-dimethyl-1-butylene, 4-methyl-2-amylene, 1,3-butadiene, 2-methyl isophthalic acid, 3-butadiene, isoprene, (2E, 4E)-2,4-hexadiene, cyclopentene, cyclohexene, 1,2-dimethylcyclopentene, 5-methyl isophthalic acid, 3-cyclohexadiene etc.The example of the alkynes that is fit to is: acetylene, propine, 1-butine, 2-butine, 3-methyl isophthalic acid-butine, 1-pentyne, valerylene, 1-hexin, 2-hexin, 3-hexin, 3,3-dimethyl-1-butine, 1-octyne, 1-n-heptylacetylene, 1-decine etc.The example of the aryl that is fit to comprises phenyl, naphthyl, tetrahydro naphthyl, 1,2-dihydroindene and xenyl.Preferably, carbon source is methane, ethene and/or acetylene.
Preferably, at 500 ℃, Ar/H 2Begin under the air-flow to carry out CVD so that metallic catalyst is reduced to metal nanoparticle.Carry out growth phase then, this stage preferably carries out under 800 ℃.
One preferred embodiment in, the preparation of compound utilize organic molysite as catalyst and acetylene as carbon source.Further preferably, utilize Fe (III) pTS as catalyst and acetylene as carbon source.
If desired, can randomly remove compound from substrate.Compound can be transferred to then in another substrate with the character that is fit to required application.Selectively, before removing from substrate, can with polymer or metal film deposition and be cured to nanotube layer above.
Use/application
Compound of the present invention and compound underlying structure are fit to multiple application.Especially, wherein the embodiment of nano-complex with electric conductivity is suitable for power conversion and field of storage, also be suitable for needing the material and facility of the large surface area material of conduction, as be used for the electrode of capacitor, hybrid battery/capacitor, ultracapacitor, battery, fuel cell, eelctro-catalyst, atmosphere storage medium, sensor, actuator, motor machine actuator, Optical Electro-Chemistry solar cell and/or be used for cell and organize the bioelectrode of electro photoluminescence.
The CNT that tangles in the Copper Foil substrate and the compound of amorphous carbon are suitable for chargeable battery.
The CNT that tangles on the aluminum foil substrate and the compound of amorphous carbon are suitable for capacitor.
The CNT that tangles on the carbon paper substrate and the compound of amorphous carbon are suitable for fuel cell.
The CNT that tangles in the film substrate and the compound of amorphous carbon are suitable for actuator.
Compound can have biocompatibility, makes it be applicable to the medical application that needs electro photoluminescence, energising or electric induction with its electric conductivity, as bioelectrode, biological fuel cell or as the used substrate of electro photoluminescence biological growth.
Compound demonstrates sufficiently high conductance, electrochemical capacitor and engineering properties, can directly implant organism alive to be used for electric induction and electro photoluminescence as electrode.Concrete application comprises that the cytothesis of pacemaker electrode, ECG electronic pads, biology sensor, muscular irritation, epilepsy control and electro photoluminescence is long.
The electrode that is used for bioimplant is made of platinum or iridium and their derivative usually.Embodiments of the present invention provide the electrical-conductive nanometer compound that can contain biomolecule.Biomolecule such as shitosan are used from human body with a lot of implants one at present.In addition, functional group can be added shitosan so that further control biological interaction.Also do not know at present the biocompatibility of CNT, but Primary Study demonstrates but and has good prospects.Therefore, very potentially produce powerful and effective neoformation electrode.These bioelectrodes also should be powerful and effective.
Description of drawings
In the embodiment of back, will mention accompanying drawing, wherein:
Fig. 1. the optical imagery of several scanning electron micrographs (SEM) and self-support type CNT/AC paper; (a) at 40cm 2After carrying out the CVD growth on the quartz plate, the digital picture of CNT/AC upper surface; (b) when when substrate is removed, the digital picture of AC layer lower surface.From image, be easy to observe photographer's reflected image, can find out the albedo of this layer; (c) remove and twist in the digital picture of the CNT/AC paper on the glass bar from quartz substrate, demonstrate the pliability and the mechanical strength on CNT/AC compound paper two sides.(d) the SEM image of film upper surface demonstrates the intensive entanglement state of CNT; (e) the SEM image of CNT/AC paper cross section; Demonstrate tangible " boundary " between AC layer (shown in the white arrow) and the carbon nano tube network upper strata; (f) the SEM image below the AC layer demonstrates tightly packed but the form of porous still.
The high resolution scanning electron micrograph image of Fig. 2 .CNT-AC juncture area demonstrates the tight contact (left figure) between outside nanometer shell and the amorphous carbon layer.Right figure is the high magnification map picture in a zone among the left figure, shows that CNT passes that the AC layer growth comes out and is not only on the AC layer.
Fig. 3. under identical experiment condition, 1mM K 4Fe (CN) 6/ 1.0M NaNO 3The cyclic voltammogram of finishing with the three-electrode battery of routine in the aqueous solution, working electrode wherein is: (a) CNT/AC paper and the MWCNT pad (mat) (NanoLab, Boston) that (b) is purchased.Because the y axle is shown as ampere/g, so can carry out the direct contrast between two kinds of different shapes.Sweep speed: 5mVs -1
Fig. 4. the digital picture of self-support type CNT/AC/ metal foiled paper and SEM image, (a) digital picture of CNT/AC on the Copper Foil, (b) the SEM image of CNT layer on the Copper Foil.
Fig. 5. prepare the step schematic diagram of CNT/AC paper according to embodiment of the present invention: (a) thin Fe (III) pTS layer (1-5 μ m) is spun on the quartz plate that cleaned; (b) be carbon source with acetylene, by hot CVD, the multi-walled carbon nano-tubes that has the high conductivity carbon-coating below making grows out; (c) self-support type paper is stripped down from quartz plate.
Fig. 6. the XRD response of following AC layer reaches the contrast with conventional carbon black sample.
Fig. 7. from (a) Fe (III) DBS, (b) Fe (III) PS and (c) the scanning electron microscopy picture of the upper surface of the self-support type CNT/AC paper that grows out of Fe (III) pTS.With identical multiplication factor display image.
Fig. 8. at 1.0M NaNO 3In the aqueous solution, be working electrode with self-support type CNT/AC paper, the cyclic voltammetric stacking chart who under different sweep speeds, obtains.Platinum electrode and Ag/AgCl have constituted conventional three-electrode battery to electrode and reference electrode.These voltammograms are used to calculate the ratio capacitance of this paper in the data of 0.2V.
Fig. 9. the digital picture of self-support type CNT/AC/ metal foiled paper and SEM image, (a) digital picture of CNT/AC on the aluminium foil, (b) the SEM image of CNT layer and (c) the SEM image of CNT/AC/ aluminium paper cross section on the aluminium foil.
Scanning electron micrograph (SEM) image of the carbon fiber paper that Figure 10 .CNT modifies shows the intensive entanglement of CNT, and described CNT has covered single carbon fiber fully, still keeps the micropore character of dominant carbon fibrous paper simultaneously; (b) (a) shown in the higher resolution image of carbon fiber; Illustration (c) is grown in transmission electron microscope (TEM) image of the single multi-walled carbon nano-tubes on the carbon fiber paper (CFP).
Figure 11. under room temperature, 900 groove/mm gratings, excite (a) Raman spectrum of not modified carbon fiber paper and (b) Raman spectrum of the carbon fiber paper modified of CNT with the 632.8nm diode laser.
Figure 12. when being used as the anode material of commercially available CR2032 button cell, CNT/CFP electrode the 1st is to the profile diagram of the 50th charge/discharge.Current density is 0.05mA cm -2
Figure 13. be deposited on discharge capacity and the cycle-index of CNT under different charge/discharge rates on the carbon fiber paper; (a) 0.05mA cm -2, (b) 0.20mA cm -2(c) 0.50mA cm -2
Figure 14. be deposited on the SEM image of the CNT nanometer net on the platinum thin slice.
Figure 15. in perilymph solution, with (a) CNT nanometer net and (b) pure platinum thin slice be 100mV s as working electrode in sweep speed -1The cyclic voltammetric stacking chart of following acquisition.The data of these voltammograms are used for contrasting electroactive in biotic environment of CNT nanometer net and platinum thin slice.
Figure 16. at 0.5M H 2SO 4In the aqueous solution (at O 2Under the atmosphere), the linear scan volt-ampere stacking chart (with respect to Ag/AgCl) who on the CNT nanometer net electrode that PPy/Co-TPP modifies, carries out hydrogen reduction.Sweep speed: 10mV s -1The porphyrin that is combined with Co (oxygen reduction catalyst) that CNT nanometer net is contained polypyrrole film is modified the oxygen reduction reaction be used for electro-catalysis.
The specific embodiment
Describe the present invention with reference to the following example, but the present invention is not subjected to the restriction of these embodiment.The instrument that uses:
Utilize Hitachi S-900 field emission scanning electron microscope method (FESEM) to obtain the SEM image.Before analysis, the sample sputter that is used for FESEM is applied chromium.
Use is furnished with He:Ne laser, and (the Jogin Yvon Horiba HR800 spectrometer of λ=632.8nm) is with the grating measuring Raman spectrum of 1800 grooves.
At room temperature utilize conventional four-point probe method to carry out conductivity measurement (JandelEngineering).
The conductivity measurement of report on average uses 5 samples.Use eDAQ e-corder multi-channel data recorder (401) and potentiostat/galvanostat (EA160) and Chart v5.1.2/EChem v2.0.2 software (AD Instruments), at 0.01M K 4Fe (CN) 6/ 0.1M NaNO 3In, be that working electrode, platinum electrode and Ag/AgCl are respectively electrode and reference electrode with CNT/AC paper, under the three-electrode system of standard, finish electrochemistry experiment.
Calculate than electric capacity, at 1.0M NaNO by the slope that mapping obtains to sweep speed of the anode current value under the 0.2V 3In, use the Ag/AgCl reference electrode, obtain the anode current value by the cyclic voltammetry under the different potential scan speed.
Use dynamic mechanical analysis instrument Q800 (TA Instruments) to carry out mechanical test.Utilize energy dispersion X-ray analysis method (EDXA) to measure AC layer Fe content with HitachiS 3000N SEM.Use Philips PW1730 diffractometer to obtain X-ray diffraction (XRD) spectrum with Cu K α radiation and graphite monochromator.
Embodiment
The spin coating instrument that use is purchased (Laurell Tech), with the speed of 1000rpm from 10% (w/w) Fe (III) TS/ ethanolic solution, with catalyst (Fe (III)/TS/DBS or/PS is spun to quartz plate, and (3mm is thick, on 4 * 10cm), forms the film of 1 μ m.Then in 60-80 ℃ normal reheating furnace, make catalyst film annealing reach 5 minutes, become deep yellowly until the film color, show that alcohol solvent evaporates.
Use commercially available hot CVD system (Atomate), make software can control air-flow, furnace temperature and sedimentation time, carry out chemical vapour deposition (CVD).(Ar, 150ml/min) flushing system 30 minutes is then at Ar (200ml/min) and H with argon gas 2(20ml/min) furnace temperature is raise, until 500 ℃.Then furnace temperature is kept 500 ℃ 10 minutes, make iron (III) be reduced into Fe nanometer particles.Temperature is elevated to 800 ℃ again, then with gas flow rate Ar (200ml/min), C 2H 2(10ml/min) and H 2(3ml/min) introduce acetylene (C 2H 2) 30 minutes, carry out the growth of carbon nano-tube film.At last, cut off acetylene and hydrogen, use Ar (150ml/min) to continue the flushing heating furnace simultaneously and be lower than 100 ℃ until temperature.Product was cooled to room temperature more than 2 hours.Very fast cooling can cause the CNT fault of construction.
The result:
By observing as can be known, the CNT film pattern that obtains from catalyst Fe (III)/TS (Fig. 1 a) with normal condition under those CNT films of growing very different.Clearly, in the CNT growth course, form the very strong layer (Fig. 1 b) of reflectivity below the carbon film.Above gained CNT/amorphous carbon (CNT/AC) paper demonstrates on quartz plate be dark layer (Fig. 1 a), below be pliable and tough shinny AC layer (Fig. 1 b).Can at an easy rate CNT/AC paper be removed from substrate, and this self-support type film can be twisted on the glass bar, and not observe the sign (Fig. 1 c) of degraded.
Utilize the whole bag of tricks to characterize CNT/AC paper.It is CNT really that scanning electron microscopy (SEM) discloses upper strata (Fig. 1 d), simultaneously, grows the CNT network of the three-dimensional structure of porous on amorphous carbon closely (AC) layer (thickness is less than 1 μ m) below the SEM image of transverse cross-sectional area (Fig. 1 e) shows.The SEM image of AC layer (Fig. 1 f) show have the nano-scale loose structure, homogeneous pantostrat closely.Nanotube in CNT bunch is that average length＞100 μ m, external diameter are the multi-walled carbon nano-tubes (MWNT) of 20-40nm.The Raman spectrum of this nanotube layer (referring to method) has produced the MWNT sample and has accepted scope interior D bands of a spectrum and G bands of a spectrum, and XRD spectrum (Fig. 6) shows that the AC layer is an amorphous carbon irregular but activation.Back one spectrum has shown 25 degree and the 42 degree peaks in the 20 degree zones, and is identical with those peaks that are purchased carbon black.The four point probe system measuring resistance of use standard, having write down CNT/AC paper is the low-down square resistance of every square 46 Ω, the AC layer thickness is about 1 μ m.This resistance value significantly is lower than the resistance of amorphous carbon (＞every square 1k Ω), and described amorphous carbon forms in CNT bunch normal CVD growth course utilizing inorganic iron (III) compound to carry out usually.Measure Fe content＜5% (obtaining this value) of AC layer by the energy dispersion X-ray analysis method.Under so little concentration, think that Fe content only can not cause the high conductivity of AC layer.
An importance of this method is selection of catalysts.The organic moiety of toluenesulfonic acid iron used herein (III) catalyst is considered to the formation of the high conductivity AC layer below the CNT upper strata is played an important role.In control experiment,, use conventional catalyst FeCl for getting rid of any system factor in the CVD system 3Replace organic catalyst.Substrate and growth parameter(s) remain unchanged.The gained material is CNT a bunch of typical conventional growth, and wherein CNT directly contacts with quartz substrate and covered (measuring square resistance is every square 1-5k Ω) by the insulating barrier of amorphous carbon.There is not the reflecting layer.
Study with other two kinds organic molysite DBSA iron (III) and pyridine-sulfonic acid iron (III), thereby more clearly describe organic moiety role in forming process.On quartz plate, successfully synthesize CNT/AC paper (Fig. 7 a and 7b) by these two kinds of catalyst.Discovery is respectively every square 86 Ω and every square 65 Ω by the square resistance of the AC layer that Fe (III) DBS and Fe (III) PS obtain.These resistance are similar to the resistance (46 Ω) of the initial CNT/AC paper that is grown out by Fe (III) pTS, but high slightly.Use different catalysts appreciable impact CNT growth, cause the length and the diameter difference of nanotube of the CNT that comprises the three dimensional entanglement network of gained very big, and loose structure is also significantly different.Fig. 7 shows, compares with those CNT that grown out by Fe (III) PS (Fig. 7 b) and Fe (III) pTS (Fig. 7 c), and (CNT that Fig. 7 a) grows out lacks and has than major diameter by Fe (III) DBS.D DBS＞D PS＞D PTS(D=diameter) and L DBS＜L PS, L PTSThe trend of (L=length) is attributable to the heterogeneity of Fe (III) organic moiety.As can be seen, have the highest loose structure bunch first-chop CNT grow out from Fe (III) pTS.
Although it most possibly is the reason that forms the AC layer that these results hint the organic component of catalyst material, further experimental results show that not exclusively by due to it.In the test that separates reflectivity AC layer, the acetylene carbon source is removed from growth course.Although it is glassy and/or the metal shape that bore hole seems outward appearance, the reflectivity of this layer is not strong.From electrical point, find that the resistance in this intermediate layer is about 5k Ω.Therefore as mentioned above, acetylene is added this process and grows nanotube, it is original more than 1/100 that this is reduced to AC layer resistance.After introducing acetylene once more, the AC layer begins to obtain the feature of CNT/AC in conjunction with paper, confirms that acetylene and organic catalyst are that the better electrode material of preparation institute is indispensable.It is predicted, because closely connect (referring to Fig. 2 a and 2b) between two carbon-coatings, so this situation has overcome the blocking effect that perplexs conventional composite.This has also explained along CNT/AC paper, the more important thing is and pass the utmost point low-resistance value that CNT/AC paper is measured gained.
Estimate that the such structure of CNT/AC paper can have significant chemical property, has supported this point and further characterize.Cyclic voltammogram (CV) shows: at low-down sweep speed (5mVs -1) under, have highly stable, very high electro-chemical activity (i pBe about 0.5A/g), given prominence to the unusual current capacity (Fig. 3) of CNT/AC paper.For clarity sake, be recorded as ampere/g, these results are compared with electroactive (Fig. 3, illustration) as the commercially available multi-wall carbon nano-tube pipe pad (NanoLab, the U.S.) of working electrode.Except peak separation (Δ E with broad p), the i of the many walls pad that is purchased pValue is approximately less than 1/10.These figure demonstrate with the many walls CNT paper that is purchased and compare, and CNT/AC paper of the present invention has long-pending (the about 48m of electroactive surface of high a lot (5 times) 2/ g) and much lower resistance (less Δ E p).Further emphasize these differences, the record cyclic voltammogram is (at 1.0M NaNO 3In, under the different scanning rates (Fig. 8)) thereby measure and to compare electric capacity.With other people report be 102F/g for activation MWNT electrode 6Be 180F/g for the SWNT compound 7Literature value compare, the ratio capacitance of the CNT/AC electrode material that calculates is 143F/g.It should be noted that the calculated value of electric capacity and peak current is underestimated owing to considered the weight of tight AC layer.The actual value of this hint nanotube layer itself should be high a lot.
Estimate to utilize the CNT electrode of the high surface area that this method generates can be to relating to charge storage and/or the transfer field has appreciable impact.Metal electrode can bring sizable commercial interest to the energy storage industry; The Copper Foil and the aluminium that is used for capacitor that are used for chargeable battery.Think that this is to go up the full carbon assembly that direct growth goes out high conductivity without Copper Foil of further modifying (Fig. 4) and aluminium foil (Fig. 9) first.Identical growth parameter(s) is used for this new substrate, and optical imagery and SEM image all show and can be observed the CNT/AC/ metallic composite.Utilize the inorganic FeCl of spin coating 3Repeat this experiment and can not produce stable film, therefore can not growing nano-tube, this has just proved conclusively the importance of organic character of Fe (III) TS to this method.When vitreous carbon was used as substrate, deposition obtained similar CNT structure.
For further specifying the chemical property of these new electrode structure brilliances, with they anodes as lithium ion battery.In typical experiment, to carbon fiber paper (a 4 * 5cm 2) homogeneous coating iron (III)-TS film.At 500 ℃, Ar/H 2Beginning under the air-flow to carry out the CVD process, is Fe nanometer particles thereby make iron (III) catalyst reduction.Next be growth phase, under 800 ℃, with C 2H 2For carbon source is carried out this stage.Observe CNT growth (Figure 10) the iron catalyst Fe conventional that finds gained with use 3O 4Those CNT that grow out are significantly different.The growth that scanning electron microscopy (SEM) (Figure 10 a-10c) has disclosed CNT layer on the CFP holder.Transmission electron microscope (TEM) (illustration) confirms that this layer is that multi-walled carbon nano-tubes by the about 30-40nm of diameter constitutes really.Raman spectrum (Figure 11) confirms that also sedimentary deposit is through abundant graphited carbon nanotube layer, respectively at 1329cm really -1And 1591cm -1D bands of a spectrum and G bands of a spectrum are arranged.Figure 10 b shows that the CNT of intensive entanglement has covered single carbon fiber (Figure 11) fully, still keeps the whole porous microstructure of carbon fiber paper simultaneously.The SEM image (Figure 10 c) in fibrous root/point zone has shown the porous character that the CNT network is high.This hints the accessibility of CNT in the electrochemistry cyclic process that deposits on each carbon fiber very high (highly accessible), has significantly increased as the electroactive surface of electrochemical apparatus important parameter long-pending.
The CNT/CFP compound that tangles has mechanical strength, and without any the sign of degraded, the following carbon-coating (forming in the CNT growth course) of this hint bonds securely with the carbon fiber network.Next, the CFP that the CNT of gained modifies can directly be used as the electrode material in the assembling electrochemical apparatus, and need not further handle.Selectively, modified CFP also can be used as template and is used for further chemical modification.
The method of record before utilizing 8, in the glove box (Mbraum, Unilab, Germany) of applying argon gas, with 1cm 2The CNT/CFP electrode is assembled in the chargeable lithium ion button battery, to be dissolved in the 1.0M LiPF of ethylene carbonate/dimethyl carbonate (50: 50) 6(Merch KgaA, Germany) carries out battery testing (neware, Electronic Co.) for electrolyte.In different constant charge/discharge current density (0.05,0.10,0.20 and 0.50mA cm -2) under, between 0.01V and the 2.00V, make battery circulate the needed time under the room temperature to reach the electromotive force limit.
Figure 12 has shown that the 1st to the 50th charge/discharge curve is (at constant current density 0.05mAcm -2Demonstrate the modified extremely stable chemical property of CNT/CFP electrode down).Curve shape and front comprise SWNT and MWNT from carbon nano-tube material 9It is observed that those are similar.Because nanostructured, the high surface area of CNT/CFP electrode uniqueness, the electrochemical stability of these charge-discharge curves have shown lithium ion and have embedded carbon nano tube structure/deviate from from the carbon nano tube structure height invertibity of process.In conjunction with mechanical strength and the electrochemistry robustness and the inherent pliability of this material, these results have shown its application possible in technical field, are not limited to lithium ion battery.
Figure 13 has shown the reversible capacity as the cycle-index function, shows that CNT/CFP is as the anode material feasibility.In the constant discharge rate is 0.05mA cm -2Down, initial reversible capacity height is 643mAh g -1The chemical property of CNT/CFP electrode has shown its inherent long-term cyclical stability, and this descends with common observed discharge capacity in the electrode cyclic process based on CNT 10Opposite fully.After 50 circulations, the CNT/CFP electrode still shows significantly, the capacity 546mAh g of completely reversibility -1(Figure 13 a), when as anode 11The time, than theoretical capacity (the 372mAh g of graphite -1) high a lot.The high reversible capacity that CNT obtained that deposits on the CFP electrode is owing to the 3-D nano, structure of its new extremely stable and porous.After the circulation, observe, do not observe the degraded of electrode, and also do not observe the change color of electrolyte through after 50 circulations.The surface area that the supposition accessibility is very high allows the lithium ion of high concentration to embed in cyclic process and deviates from.This result with by other value that obtains based on the electrode structure of CNT 12Opposite fully.
Use different charge/discharge rates and carry out Primary Study (Figure 13 b and Figure 13 c) to investigate their abilities under high power.When charge/discharge rate by 0.05mA cm -2Improve 10 times and reach 0.5mAcm -2The time, although the charge/discharge capacity value is lower than those values of record under the low current density, observed result still demonstrates the high reversible capacity 338mAh g based on the CNT network -1This has hinted that such CNT/CFP electrode also is useful on the potentiality of high-power battery equipment as anode material.
Estimate to utilize the high surface area CNT electrode that this new method generates can be to relating to charge storage and/or the transfer field has appreciable impact.Metal electrode can bring sizable commercial interest to the energy storage industry, for example, is used for the Copper Foil and the aluminium that is used for capacitor of chargeable battery.Fig. 4 has shown the versatility of this method, wherein shown CNT/ carbon-coating compound (growth parameter(s) of record before utilizing) can be directly generation and need not further modify this substrate in copper and other conduction and non-conductive substrate.In optical imagery shown in Figure 4 and SEM image, can be observed CNT/ carbon-coating/Cu composite.In Fig. 4 a, catalyst only is coated in half substrate in order to clearly to demonstrate following substrate.Utilize the inorganic FeCl of spin coating 3Repeat this experiment and can not produce stable film, therefore can not growing nano-tube, organic character of having proved conclusively Fe (III) TS is to the very important this viewpoint of this method.Contact resistance between carbon-coating and the Copper Foil is about 1.0-2.0 Ω, and the resistance between CNT network and the Copper Foil is in identical scope.
A major advantage of this new method is the CNT/ carbon-coating network that all can produce three-dimensional structure in any substrate, as long as satisfy following two conditions: i) this substrate can withstand the growth temperature (＞600 ℃) of heating furnace; Ii) organic catalyst forms stable film.These new CNT substrates can further be handled and can be directly used in the manufacturing electrical devices, or form conduction and pliable and tough template is used for further modification.
A major advantage of this method is all to produce these CNT/AC films in any substrate, as long as satisfy following two conditions: (i) this substrate can withstand the growth temperature (＞600 ℃) of heating furnace; (II) organic catalyst (Fe (III) TS) forms stable film.The metal forming that these CNT modify has only several micron thickness, can further handle being directly used in the manufacturing electrical devices, or forms conduction and pliable and tough template is used for further modification.
The method that is used to prepare these high surfaces CNT electrode is simple, economical and be easy to large-scale production.Expectation CNT electrode can be used as pliable and tough and thin ultracapacitor and be used as the anode material in Li-ion rechargeable pond, and in seeking the process of more effective nanometer biotechnology, need also to be used to the field of electrode to contact with living things system of nanostructured.
It will be understood by those skilled in the art that without departing from the spirit and scope of the present invention and can make multiple modification.
In the specification of claims of the present invention and front, unless context need explain in addition to language performance and necessary application, word " comprises " or its distortion is open expression, promptly, existing feature is made clear, but and be not precluded within the various embodiments of the present invention and exist or additional further feature.
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Claims (21)

1. a nanostructured composites comprises the nanotube network that is incorporated into carbon-coating.
2. compound according to claim 1, wherein said nanotube network is partially submerged into described carbon-coating at least.
3. compound according to claim 1, described compound are conductions and/or have biocompatibility.
4. compound according to claim 1, wherein said nanotube are the non-orientation nano pipes that can form the three dimensional entanglement network.
5. compound according to claim 4, many walls nanotube that wherein said nanotube is non-orientation.
6. compound according to claim 1, wherein said nanotube is a CNT.
7. compound according to claim 1, wherein said carbon-coating are activated carbon layer (CL).
8. compound according to claim 1, described compound further comprises substrate, obtains the nanostructured composite basal structure thus.
9. compound according to claim 8, wherein said carbon-coating is connected with described substrate.
10. compound according to claim 9, wherein said substrate are conductions or nonconducting.
11. compound according to claim 10, wherein said substrate are metal or polymeric material.
12. compound according to claim 8, wherein said nanotube, carbon-coating and/or substrate are through chemical modification.
13. relating to, compound according to claim 12, wherein said chemical modification connect biomolecule, catalyst and/or additional conductors.
14. a method that is used to prepare nanostructured composites or nanostructured composite basal structure may further comprise the steps:
I) metallic catalyst is deposited in the substrate;
Ii) by chemical vapor deposition (CVD), the nanotube network that has carbon-coating below making grows out from described suprabasil catalyst, forms the nanostructured composite basal structure; And
Iii) randomly, separate described nanostructured composites from described substrate.
15. method according to claim 14, wherein said metallic catalyst are organo-metallic catalyst or inorganic metal catalyst.
16. method according to claim 14, the metal of wherein said metallic catalyst is selected from palladium, iron, rhodium, nickel, molybdenum and cobalt.
17. method according to claim 15, wherein said organo-metallic catalyst are p-methyl benzenesulfonic acid iron (III) (Fe (III) pTS), DBSA iron (III) (Fe (III) DBS), pyridine-sulfonic acid iron (III) (Fe (III) PS), camphorsulfonic acid iron (III), nickel acetate (II), nickel acetylacetonate (II), cobalt acetate (II) or acetylacetone cobalt (II).
18. method according to claim 14, wherein said CVD growth relates to the use of carbon source.
19. goods comprise all or part of of nanostructured composite basal structure that nanostructured composites that claim 1 limits and/or claim 8 limit.
20. goods according to claim 19, described goods conduct electricity.
21. goods according to claim 20, described goods are selected from the electrode that is used for energy storage and conversion; Electrode as fuel cell, atmosphere storage medium and sensor; The electrode that is used for biomedical sector, environmental area and industrial circle; Be used for the deionized electrode of electrochemistry; Bioreactor; The platform or the support that are used for cell cultivation or organizational project; And chemistry and gas separator.
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