CN100528547C

CN100528547C - Single-walled carbon nanotube-ceramic composites and methods of use

Info

Publication number: CN100528547C
Application number: CNB2004800182678A
Authority: CN
Inventors: 利安德罗·鲍尔詹诺; 丹尼尔·E·里萨斯科
Original assignee: Individual
Current assignee: Individual
Priority date: 2003-04-28
Filing date: 2004-04-28
Publication date: 2009-08-19
Anticipated expiration: 2024-04-28
Also published as: MXPA05011574A; CN1819916A; EP1626862A4; EP1626862A2

Abstract

Composites of single-walled carbon nanotubes (SWNTs) and a ceramic support (e.g., silica) comprising a small amount of catalytic metal, e.g., cobalt and molybdenum, are described. The particle comprising the metal and ceramic support is used as the catalyst for the production of the single-walled carbon nanotubes. The nanotube-ceramic composite thus produced can be used ''as prepared'' without further purification providing significant cost advantages. The nanotube-ceramic composite has also been shown to have improved properties versus those of purified carbon nanotubes in certain applications such as field emission devices. Use of precipitated and fumed silicas has resulted in nanotube-ceramic composites which may synergistically improve the properties of both the ceramic (e.g., silica) and the single-walled carbon nanotubes. Addition of these composites to polymers may improve their properties. These properties include thermal conductivity, thermal stability (tolerance to degradation), electrical conductivity, modification of crystallization kinetics, strength, elasticity modulus, fracture toughness, and other mechanical properties. Other nanotube-ceramic composites may be produced based on AL2O3, MgO and ZrO2, for example, which are suitable for a large variety of applications.

Description

Single-walled carbon nanotube-ceramic composites and its using method

The statement of relevant federal sponsored research or exploitation

Do not have.

Background of invention

The present invention relates to field of carbon nanotubes, especially but relate to composite and the goods that contain SWCN without limitation.

CNT (being also referred to as carbon fibrils) is the seamless pipe of graphite flake, has full fullerene pipe cap (full fullerene cap), what people at first found is multilayer concentric pipe or multi-walled carbon nano-tubes, has found SWCN existing under the transition-metal catalyst situation afterwards.CNT has good application prospects, comprises electronic device, high-strength material, electric field transmitted, SEM filament and the gas storage material of nanoscale.

Usually, because SWCN is compared with multi-walled carbon nano-tubes, defective still less and therefore similar with diameter multi-walled carbon nano-tubes phase specific strength is higher, electric conductivity is better, so have preferred property in these are used.SWCN is compared the possibility that defective occurs with multi-walled carbon nano-tubes little, this be because multi-walled carbon nano-tubes by under when accidental defective occurring, preserving forming bridge between the unsaturated carbon bond, and the SWCN shortage is used for compensating the adjacent wall of these defectives.

SWCN has superior chemistry and physical property, has brought a large amount of potential application.

But can these novel SWCNs that obtain actual techniques requirement and form remain a problem.Still need to prepare the extensive technology of high-quality SWCN, and still need to be applied to the appropriate format of the required SWCN of various technology.The present invention is just in order to satisfy the demand that these relate to.

The accompanying drawing summary

Fig. 1 shows the schematic diagram of a plurality of reactors that can be used for preparing goods of the present invention.

Fig. 2 shows has two kinds of different silica composition (silica gel-60 and Hi-

) the reactor B 2 downstream CO of two kinds of Co: Mo (1: 3)/SiO 2 catalyst (2% metal load) ₂The graph of a relation in concentration and reaction time.Be reflected at 850 ℃ and carry out, air speed is 67000h ^-1

Fig. 3 is the scanning electron micrograph of nanotube-ceramic composite articles, has shown the SWNTS bundle that is inserted between the silica dioxide granule.

Fig. 4 shows at different temperatures and H ₂The I of the compound for preparing under the concentration and V relation curve.

Fig. 5 is the TEM image of the MCM-41 carrier material of preparation.

Fig. 6 is the XRD figure spectrum as the MCM-41 of Fig. 5 preparation.

Fig. 7 is I and the V relation curve that adopts the nanotube-ceramic complexes of various silica supports preparations.

Fig. 8 is at the I of 750 ℃ and 850 ℃ synthetic Aerosil 380 nanotubes-ceramic complexes and V relation curve.

Fig. 9 is I and the V relation curve with two kinds of nanotube-ceramic complexes of different metal load (2% and 6%).

Figure 10 is composite and I and the V relation curve of SWNTS after different purification processes.

Invention is described

The present invention relates to SWCN (SWNTs) and ceramic monolith () composite for example, silica, wherein said carrier comprises the little amount of catalyst metal, for example, cobalt and molybdenum.Comprise the catalyst of the particle of metal and ceramic monolith as the preparation SWCN.Nanotube-ceramic complexes of making like this can need not further to purify just to use with " preparation state ", thereby has tangible cost advantage.In a certain application is launched such as the field, to compare with the CNT of purifying, this nanotube-ceramic complexes has also demonstrated more superior performance.

And, for example there is not the silica supports of micropore by use, such as precipitated silica and fumed silica (smoked silicon), the structure of ceramic composition to be adjusted, the SWNTs quality can significantly improve.Based on comprising Al ₂O ₃, aluminium oxide, MgO and ZrO that La is stable ₂Carrier material, can prepare other nanotube-ceramic complexes, and these materials for example are suitable for numerous application.These nanotube-ceramic complexes can make polymer performance improve in being attached to polymeric substrates the time.These character comprise thermal conductivity, heat endurance (aging tolerance limit), electric conductivity, crystallization kinetics correction, intensity, coefficient of elasticity, fracture toughness and other mechanical performance.To describe these and other characteristic of the present invention and performance below in detail.

In one embodiment, by the metallic solution impregnated carrier component (for example, silica) with different specific concentrations, preparation provides the catalyst of the ceramic composition of nanotube-ceramic complexes of the present invention.For example, flood the bimetallic catalyst (referring to U.S. Pat 6333016, its full content openly is incorporated herein by reference at this) that various silica supports obtain selected composition, prepared Co: Mo/SiO by the aqueous solution with cobalt nitrate and ammonium heptamolybdate ₂Catalyst.The liquid/solid ratio remains on the initial humidity condition, and is all different to each carrier.Total metal load is 0.1 weight %-20 weight % preferably.Behind the dipping, catalyst is preferably at first dry in air at room temperature, then in baking oven in 120 ℃ of dryings, at last in moving air in 500 ℃ of calcinings.

SWNTs can for example prepare on these catalyst in fixed bed reactors, moving-burden bed reactor or the fluidized-bed reactor in different reactor known in the art.Fluidized-bed reactor can be with for example intermittent mode and continuous-mode operation.

This work has been adopted four laboratory scale reactors to study and has been optimized CO: Mo/SiO ₂The reaction condition (Fig. 1) of series.First reactor (A) is made of the horizontal quartz ampoule of 1 inch of diameter, has wherein placed porcelain boat, and the 0.5g calcined catalyst is arranged in the porcelain boat.This is the typical reactor configuration of often seeing in the synthetic document of relevant CNT.The second and the 3rd reactor (B1 and B2) is respectively that diameter is the typical quartz fixed bed reactors of 1/8 inch and 1/4 inch.Reactor B 1 is loaded with the 0.05g catalyst, when its with 400000h ^-1During the air speed operation, be considered to differential reactor.Reactor B 2 contains the 0.5g catalyst, in 67000h ^-1Air speed running.At last, the 4th reactor (C) is a fluidized-bed reactor.

In all cases, catalyst carried out prereduction and (for example, is exposed to H at 500 ℃ before being exposed under the reaction condition ₂Down).(for example, CO) before, catalyst is heated to reaction temperature (700 ℃-1050 ℃) in He being exposed to carbonaceous gas.Subsequently, introduce carbonaceous gas or gasified liquid.After 1-600 minute reaction time, reactor cleans and cool to room temperature with He given.

For continuous or semicontinuous system, can be in the reactor that separates pretreatment catalyst, for example, for the more substantial catalyst of preliminary treatment uses in the SWNT unit after making these catalyst to store.Adopt this new methodology, fluidized-bed reactor can be in the reaction temperature continued operation, thereby removes the preliminary heating and cooling step in the reaction treatment.

By changing reaction condition, the disproportionation by CO in preferred range 700-950 ℃ (resolves into C and CO ₂), the generation of catalyst selectivity SWNTs (, open being incorporated herein by reference in full) at this referring to U.S. Patent Application Serial No.10/118834.The synergy of Co and MO is to the performance of this catalyst very important [4].When separately using, these metals do not have effect; They promptly do not have activity (Mo separately) not have selectivity (Co separately) yet.Have only when these two kinds of metals to be present in simultaneously when existing close Co-Mo to react to each other on the silica supports, this catalyst is just effective.Research had been carried out on the basis of this catalyst selectivity.

Without wishing to be bound by theory, we believe that the selectivity to generating the SWNT product depends on the Mo oxide species strongly to Co ²⁺The stabilization of species will make an explanation below.We find that the interactional degree of Co-Mo is Co in the catalyst: the function of Mo ratio, the different phase in the catalyst life phase has different form [4].When being in calcined state, the form of Mo is finely disseminated Mo ⁶⁺Oxide.The state of Co depends on Co strongly: the Mo ratio.When Co: Mo when low, the Mo in Co and the surface C o molybdate structure interacts.When Co: Mo when high, Co forms non-interacting Co ₃O ₄Phase.Carry out reduction treatment process at the follow-up hydrogen that places, non-interacting Co is reduced into metal Co mutually, and the species of Co molybdate shape remain finely disseminated Co ²⁺Ionic state.Co-Mo interacts and has suppressed to form the Co sintering that usually takes place under the required high temperature at CNT.When having big Co particle, the unfavorable carbon of the form that generated (in most cases being Graphite Nano Fiber).As a comparison, when Co bunch little to including only a few atomic time, only generate SWNT[2,4].When metallic atom begins to reunite under gaseous state CO condition, a forming core phase is arranged, during nanotube do not grow.Forming core relates to the Co atom and ruptures from the interaction of itself and Mo oxide, and this moment, the latter became the carbide of dehydrogenation.Post-rift surface migration causes Co to be agglomerated into mobile bunch, bunch continues to grow up under the bombardment of CO molecule.Part in these molecules is decomposed and is begun to rearrange (forming core), and till forming favourable structure (plumule), this structure triggers and forms nanotube.After plumule formed, the follow-up combination of carbon and SWNTs formation meeting perhaps only were subjected to the control of material migration to carry out fast.Therefore, can reach a conclusion, the growth of every pipe is subjected to the restriction of forming core, is subjected to the control of material migration after forming core is finished.For this reason, we have observed the deposition of carbon on solid catalyst and have continued a few hours, although the growth of individual tubes only expends the time of millisecond.The diameter of pipe determined by the size of plumule, so, the diameter of nanotube can be under reaction condition by the size Control of metal cluster.

Adopt non-mesoporous silica to improve the selectivity of SWNT as carrier material

The growing state of system research SWNT under the differential responses condition confirmed that mass transfer limit has consequence in quality and the yield aspects of decision SWNT.By adjusting reaction condition and revising reactor configurations, outside mass transfer limit is minimized.On the other hand, minimize, can adjust the air hole structure and the particle size parameter of catalyst granules in order to make the diffusion inside problem.Generally speaking, granule that pore size is bigger or little non-porous particle can be used for reducing inner mass transfer limit.But if do not revise the configuration of reactor, it is a lot of that particle size is reduced.Because in order to keep the CO conversion ratio hang down the high air speed of needs, and need high superficial velocity for outside mass transfer limit is minimized, thus significantly reduce the particle size of catalyst can be remarkable pressure drop in the increase fixed bed reaction system.Therefore, preferably adopt fluidized bed reaction system to replace.In this reactor, can adopt than fixed bed reactors thin the particle of Duoing.In some cases, can use the same thin particle with powder.Under those situations, can be by existing technology, such as stirring and vibration, avoid the reunion between the particle and the bonding of bonding and particle and wall, these prior arts have been destroyed intergranular bonding and have been improved flowability.Stand-by particles of powder size preferably drops under the category-A classification of Geldart classification.

Another kind can be used to make the minimized method of contingent diffusion-restricted in the carbon nano tube growth process, is to make along with reaction has high surface area more to be exposed to the catalyst granules generation original position division of gas phase.This method is a method commonly used in the polymerization technique, is used for improving and modification kinetics [25].By using the specific support that may need or not need particular adhesive, realized the original position division of catalyst.Such catalyst can use in two ways.For example, along with the growth of nanotube, breakage of particles exposes the surface that makes new advances, thereby increases the total carbon productive rate that adopts this catalyst to obtain.Perhaps, binding agent used in the carrier decomposes under reaction condition, generates thinner powder in reactor.Use thinner powder can improve final carbon productive rate equally.

The microporosity that we have observed silica support is the partly cause that generates imperfect form carbon in final catalysate.The physical obstacle that mass transfer limit in these micropores and SWNT grow in these holes may be to cause the nanotube reasons for quality decrease.By studying the influence of the maximum temperature that in the catalyst pre-treatment step, reaches, confirmed this hypothesis.Two reactions adopt Co: Mo (1: 3)/silica gel 60 (2% metal load) catalyst to carry out two hours in same temperature (750 ℃).Under a kind of situation, adopt conventional program, catalyst is preheating to 750 ℃ in He.Under second kind of situation, catalyst at first is preheating to 950 ℃ (thereby reducing microporosity), is cooled to 750 ℃ then.A kind of preliminary treatment in back has obtained much better product, and mass parameter c is 0.83, and the c of first kind of situation only is 0.62 (mass parameter c is along with the minimizing of amorphous carbon quantity in the product increases).But, the diameter of gained SWNT distribute and the carbon productive rate on find difference.

The structure of silica suffers damage in the temperature of height to 950 ℃, so the micropore of this carrier tends to cave in.The average preliminary treatment aperture of silica gel 60 is 6nm.Single-walled nanotube can not be grown in than the much smaller pore of this value, so these pores can cause forming amorphous carbon.When because when the minimum pores of 950 ℃ of preheatings caved in, the formation of amorphous carbon descended, the quality increase of material.

In order to confirm the performance of this hypothesis and improvement catalyst, different silica supports have been studied with different air hole structures.Used new SiO ₂Be precipitated silica " Hi-

-210 " (can available from PPG), this material have micro-pore.

Adopt Hi-

The catalyst that contains Co: Mo (1: 3) (the metal load is 2%) of-210 silica preparation has carried out three experiments with 950 ℃ of employings with above-mentioned identical program at 750 ℃, 850 ℃, and Boudouard reaction 2 hours is carried out in experiment.The 4th reaction also carried out at 750 ℃, but used catalyst is the catalyst of crossing 950 ℃ of heat pre-treatment.The result of gained mass parameter c and carbon productive rate is summarised in table 1 li, with some is different as a result by silica gel 60 gained.When carrying out preliminary treatment and when reaction at 750 ℃ or 850 ℃, c or carbon productive rate all not have significantly to increase, but when carrying out preheating and when reacting at 950 ℃, these two parameters all significantly diminish (becoming 0.80 and 2.0% respectively).Second it is worth noting at 750 ℃ and 850 ℃ (c=0.97) even the SWNT quality of making far above adopt silica gel 60 the SWNT of gained under the optimum operation condition (c=0.83) (referring to before discussion, promptly silica gel 60).

Table 1-adopts Co: Mo (1: 3)/SiO in reactor B 2 ₂-Hi- Catalyst) the SWNT quality and the output of gained.Be reflected at and carried out under the 5.8atm 2 hours.

The result of The pre-heat treatment is also very important.Aforementioned employing silica gel 60 significantly increases in the c of 950 ℃ of preheating gained value as catalyst carrier and with catalyst, when using the low silica (Hi-of microporosity

) time do not observe.

These results show that the microporosity of silica gel 60 is to form the partly cause that has reduced the amorphous carbon of SWNTS selectivity (that is the c of reduction) at least.The increase of mass parameter c and micro-pore caving under higher temperature is relevant when reaction temperature increases.℃ observed similar quality when catalyst warm-up to 950 and improved, and when adopting Hi-

This temperature effect disappears during-210 silica (microporosity is low), has all supported this hypothesis strongly.

Allow the people is interested to be, adopt Hi-

-210 observed another differences are to be 950 ℃ carbon productive rate very low (only 2wt%) in reaction temperature.And quality (that is selectivity) is (c=0.8) also well below in the c of 750 ℃ and 850 ℃ gained value.These observed results show catalyst because sintering has had higher passivation rate.The surface area of carrier is lower, and may making more, multi-catalyst is exposed under this sintering effect.

It should be noted that the carbon productive rate is slightly higher than the situation of using silica gel 60 when being reflected at 750 ℃ and 850 ℃ when carrying out 2 hours.But, adopt Hi-

The productive rate that obtains during-210 long-time reactions is similar, and this shows W-response speed difference in fact in both cases.And, when producing CO in the online character spectrum subsequently ₂The time (referring to Fig. 2), find in the beginning of reaction 30 minutes, to adopt Hi- -210 reaction rate is 2 times of employing silica gel 60 at least.Subsequently, CO ₂Generation significantly slack-off, becoming is lower than the situation that adopts silica gel 60 catalyst.This observed result shows that the main generation of SWNTS is the beginning of reaction 30 minutes period.

These observed results for interior diffusion-restricted the preparation SWNTS W-response speed strong evidence is provided.Therefore, as mentioned above, the growth of SWNTS self occurred in millisecond time, and the forming core step of nanotube is the step of expansion speed restriction in being subjected to.In this related difference phenomenon of forming core step, relatively may affected phenomenon be the release of cobalt bunch.

Katura curve and Raman spectrum are used for studying the diameter distribution of preparation SWCN and the relation of reaction temperature.Adopt 633nm and 514nm laser to obtain Raman spectrum.Be reflected at and carried out in the reactor B 22 hours, adopt the Co of metal load 2%: Mo (1: 3)/Hi- Silica.The reaction condition of carrying out is 5.8atm and 750 ℃, 850 ℃ and 950 ℃.When silica gel 60 was used as carrier, along with the rising of reaction temperature, the diameter of gained SWNTS was bigger, and diameter distributes wideer.For example, be about 0.9nm in the average diameter of the SWNTS of 750 ℃ of reaction temperatures preparation, and at the about respectively 1.1nm of SWNTS diameter and about 1.4nm of 850 ℃ and 950 ℃ reaction temperature preparations.

At last, observe when it and adopt other atresia silica (for example, fumed silica

380 Hes

90 (can available from Degussa company) and Cab-O-

(can available from Cabot company)) obtained analog result during as catalyst carrier.

Nanotube-ceramic complexes described herein can prepare by comprising following carrier material: contain fumed silica nano particle (for example, diameter is 10-20nm), precipitated silica, the silica that comprises silica gel, aluminium oxide (Al ₂O ₃), aluminium oxide, the MgO (magnesia) that La is stable, the mesoporous silica material that comprises SBA-15 and Mobil Crystalline Materials (comprising MCM-41), zeolite (comprising Y type, β type, KL type and modenite) and ZrO ₂(zirconium dioxide).Catalyst in one embodiment comprises cobalt and molybdenum (or other catalytic metal), has constituted the ceramic catalyst particle that preferably reaches 20wt%.Ceramic catalyst can further comprise for example chromium, or other metal comprises Fe, Ni or W, or other is listed in U.S. Patent No. 6333016 or No.6413487 or U.S. Patent Application Serial NO.60/529665 those, and these patents openly are incorporated herein by reference in full at this.Every kind of nanotube-ceramic complexes preferably includes the carbon up to 50 weight %, for example 1-10% of composite gross weight.The overall diameter of preferred at least 50% SWNTS is 0.7nm-1.0nm, more preferably at least 70%, still more preferably at least 90%.In another embodiment, the overall diameter of at least 50% SWNTS is 1.0nm-1.2nm, more preferably at least 70%, most preferably at least 90%.In another embodiment, the overall diameter of at least 50% SWNTS is 1.2nm-1.8nm, more preferably at least 70%, most preferably at least 90%.

Placing catalytic metal on it is not CNT with the carrier material that forms metal catalyst particles.Only after being exposed to reaction condition, this metal catalyst particles just forms CNT.

Implement

Made herein CNT-catalyst support compositions can be used for for example electron field emitter, the polymer filler in order to improve polymer machinery and electrical property, the coating filler that is used to improve coating machine and electrical property, the filler of ceramic material and/or the component of fuel cell electrode.These only are the example how present composition can use certainly, and its purposes is not limited thereto.Used these will be described in further detail below.

Purposes in FED

Because have excellent emission characteristic, high chemical stability and splendid mechanical performance, SWCN has received suitable concern on as the field emission device material.Even the application that extensive work attempts to realize nanotube has been done in the whole world, but only a part has demonstrated the potentiality that are of practical significance.Wherein, FED (FED) is one of at first business-like application.FED is characterised in that excellent display performance, such as the color of fast response time, wide visual angle, wide region operating temperature, similar cathode ray tube (CRT) sample, ultra-thin characteristic, low cost and low energy consumption.The FED technology is to be used for diagonal greater than 60 " one of the most promising method [5] of direct field of vision display.At present, there is not perfect technology to come the vertically aligned nanotube of low-temperature original position growth in the large-area glass substrate.A kind of interchangeable technology is to use the separately nanotube of preparation, uses deposition techniques such as method for printing screen then on negative electrode.The deposition of the mixture of nanotube and dielectric nano particle (DNP) causes emission characteristics be improved [for example, referring to list of references 6 and United States Patent (USP) NO.6664722 and 6479939].This research and high-quality nanotube-ceramic complexes described herein perfectly combine.Nanotube-ceramic complexes is particularly suited for this application, because SiO ₂Be form of nanoparticles (dielectric) and shown extraordinary result (referring to embodiment 1) in this respect.

Zhi Bei nanotube-ceramic complexes is shown in the embodiment shown in Figure 3 herein.From physically separating, this has and benefits a reflective application nano particle of silica supports with the nanometer tube bundle.The nanotube of nanotube-ceramic complexes of the present invention and purifying is compared with the pure physical mixture of SiO2, has at least two advantages.

Particularly, it is much higher that silica separates the efficient of nanometer tube bundle, and the cost of composite of the present invention is than the low a plurality of magnitudes of purifying SWCN.

Purposes in order to the filler of the mechanical performance of improving polymer and electrical property

Thermoplastic and thermosetting material have been filled the graininess strengthening material such as SiO ₂Improve mechanical performance, hot property and chemical property.When strengthening material was the yardstick of nanometer scale, the improvement of these character was conspicuous.Therefore, fumed silica (can buy the granularity of 10-20nm) is used as the strengthening material of PVC, silicone, acrylic resin [7-11] and vulcanized rubber [12] usually.The thickener [15] that also is used for dental filler [13], Electronic Packaging [14] and coating and coating as composition material.

SWCN has had the electrical property and the mechanical performance of nonesuch, and this makes it become good candidate material, is attached to and obtains high-intensity conducting polymer in the polymer substrate.But,, need nanotube to be dispersed in the polymer substrate well in order to utilize the performance of CNT.Ideal situation is, dispersion should make that nanotube is single to be embedded in the polymer substrate.But,, up to the present also do not develop the technology that realizes that fully successfully this yardstick disperses though many scientists are studying in this field.

Nanotube-ceramic complexes of the present invention has been utilized simultaneously the advantage of nanoscale silica and SWNTS as polymer filler.In addition, develop SiO ₂The dispersion technology that is attached in the different polymer substrates still can be used for this nanotube-ceramic complexes, so strengthened the dispersion of SWNTS simultaneously.Dispersion can be carried out in the molten state of polymer, also can carry out in time in the solvent of polymer dissolution in various activity.Active solvent can be the low-molecular-weight heat reactive resin, and they and matrix polymer fusion also can improve processing conditions (for example, fusion viscosity and processing temperature).And, by generating grafting site, SiO ₂Surface chemistry can be easy to change being attached in the concrete polymer substrate, described grafting site can be as the fixing point that promotes the polyalcohol-filling material bonding and/or as the site of beginning original text polymerization.

Purposes as the catalyst of in-situ polymerization

It is " in-situ polymerization " (referring to U.S. Patent Application Serial No.10/464041, its content is incorporated herein by reference at this open full text) at the new technique that polymer substrate at utmost disperses that being used for of our invention makes SWNTS.The character that we have found that the SWNTS-polymer composites for preparing by this technology is than good a lot [16,17] of being mixed gained by same polymer and nanotube simple physical.We be used for SWNTS in conjunction with and the method that is distributed in the polymer be the technology that is called micro emulsion gel polymerization, this technology is the existing method of the narrow polymer beads of prepared sizes distributed pole.The advantage of this method is, compares with conventional emulsion polymerization, makes reactive hydrophobic droplet be stabilized in surfactant required in the water-bearing media and significantly reduces.This method has also been eliminated the monomer that occurs and has been transferred to advanced dynamic in the micella in conventional emulsion polymerization.Polystyrene that is filled with SWNTS (SWNTS-PS) and styrene-isoprene composite by this method preparation have distinguished physical features, such as: evenly be colored as black; High-dissolvability in toluene and oxolane (THF); And semiconductor is to the behavior of resistive electricity.

In-situ polymerization technology also can be used for realizing the fine dispersion of nanotube-ceramic complexes of the present invention in different substrates.And, by before the preparation nanotube, activator being joined in composite or the exposed catalyst, can optionally customize these nanotube-ceramic complexes for the in-situ polymerization of concrete polymer.For example, we have developed SWNTS/SiO ₂Composite, having mixed with chromium to work it in the ethene in-situ polymerization.Adopt PhillipsCr/SiO ₂Preparation of Catalyst ground polyethylene accounts for the 20%[18 of world's polyethylene production].Because this catalyst need keep activating under high temperature CO could be to polymerization effective [19], so the nanotube-ceramic complexes of the present invention that is doped with chromium has been in the state of activation and has been convenient to vinyl polymerization after by the CO division growth of nanotube taking place.In fact, at the growing period of SWNTS, this catalyst is handled under the pure CO of high temperature.This chromium-doped nanotube-ceramic complexes comprises the catalyst of effective polymerization.

Be used as the purposes of the filler of ceramic material

Conventional pottery is hard but crackly material.CNT added in the ceramic material can significantly improve its resistance to fracture, and the thermal conductivity and the electrical conductivity that improve pottery.These new materials finally can substitute conventional pottery or even metal in countless products.For example, scientist mixes alumina powder and SWCN, in conjunction with heat, pressure and current impulse particle is brought together then.The method that is called spark-plasma sintering and was attempted to prepare the used normal sintering technology of nanotube reinforced composite material in the past and was compared, and operating temperature is lower.When the researcher prepared nanotube content account for its material 5.7% ceramic the time, the fracture toughness of product is increased to more than two times of pure alumina pottery.When CNT accounted for 10 volume %, ceramics toughness almost became 3 times.

Because the price height of SWCN, it is believed that the purposes the earliest by the pottery of these material preparations may be that cost is placed on deputy application, such as airborne vehicle and medicine equipment.But nanotube-ceramic complexes of the present invention can be easy to be used for strengthening these potteries, and can be further used for wider scope because its cost is low.

Purposes in fuel cell electrode

Because fossil fuel are to environment and geopolitical influence, current to reduce use craving for of fossil fuel powerful promote that fuel cell becomes internal combustion engine allow the interested substitute of people.The basic element of character of fuel cell is ionic conductivity electrolyte, negative electrode and anode.Fuel ratio such as hydrogen (or methane) enter the anode chamber, discharge electronics at this and become proton, and diffusion of protons is reacted and consume electrons at this and oxygen to cathode chamber.Electrolyte serves as the barrier layer of gas diffusion, but allows ion transfer.

In dissimilar fuel cells, polymer dielectric film (PEM) fuel cell all is preferred for most of portable systems usually.Their running is by carrying out hydrogen ion by the hydration zone transmission of sulfonated polymer.Because the high conductance of film, they can be at cold operation (＜100 ℃).And recent development has allowed to use leads the proton film, and such as Nafion (ionomer)+silica+PW (based on the heteropoly acid of phosphorus tungsten), these films can be " anhydrous " with operation under the low temperature.Be accompanied by the development of dielectric film, the development of the electrode that performance is improved is also being paid close attention in the whole world, to improve kinetics, reduce P t loading and to improve anti-CO poisoning capability.

It is important problem in the PEM fuel cell that the CO of anode poisons.By using Ru, Mo, Sn or WO _xWith the Pt alloying, some up-and-coming results have been obtained.After deliberation some substrates, make the maximization of the degree of scatter of Pt (eelctro-catalyst) and electrode validity.For example, Bessel etc. [20] after deliberation with the carrier of Graphite Nano Fiber as the platinum grain fuel cell electrode.They compare various Graphite Nano Fiber and Vulcan carbon (XC-72).Discovery is carrier and the catalyst be made up of 5wt% platinum with the Graphite Nano Fiber, compares with the catalyst that with Vulcan carbon is carrier and about 25wt% platinum, and is active suitable.And observing with the Graphite Nano Fiber is that the metallic particles of carrier is compared with conventional catalyst, and the sensitiveness that CO is poisoned obviously diminishes.Improvement on this performance comes from the particular crystal orientation that can take when Pt disperses on Graphite Nano Fiber.Equally, Rajesha etc. [21] have been found that with the multi-walled carbon nano-tubes combination of the Pt and the W that are carrier, and are comparing of carrier with Vulcan carbon, and it is a lot of to make that the electrode efficiency of methanol fuel cell improves, and this is higher owing to Pt metal degree of scatter.

All these results show that the SWCN (perhaps separately SWNTS) of nanotube-ceramic complexes of the present invention compares with multi-walled carbon nano-tubes or Graphite Nano Fiber, have more high surface and more perfect structure, so should be more effective.In addition, compare with the carbon of other form, the high electrical conductivity of SWNTS makes final electrode have favourable characteristic.

Purposes in solar cell

The researcher of Cambridge University's engineering department [22] has developed optoelectronic device, and is better than plain optoelectronic device performance when doped single-walled carbon nanotubes.By on applying, depositing the organic film that contains SWNTS, prepared nanotube diodes by the glass substrate of tin indium oxide (ITO).Aluminium electrode heat volatilization under vacuum then forms sandwich construction.CNT and polymer poly (the 3-octyl group thiophene) interaction between (P3OT) makes polymer be dissociated into separately independently electric charge by the exciton that light produces, and operation gets up to be more prone to.

The operation principle of this equipment is that the interaction of CNT and polymer makes the photoproduction exciton in the polymer separation of charge occur, and electronics effectively is transported on the electrode by nanotube.Electronics moved nanotube length and skips or pass potential barrier then and arrive next nanotube.Thereby cause electron mobility to increase, and make charge carrier keep balance to the transmission of electrode.In addition, the researcher finds that the conductance of composite brings up to 10 times, and showing has penetration route in the material.Also improved the photoelectric properties of equipment with SWNTS doping P3OT polymer diode, photoelectric current has been brought up to surpassed two orders of magnitude, open loop circuit voltage doubles.

Nanotube-ceramic complexes of describing can be very useful for this application now, because in order further to improve the performance of these equipment, needs film preparation and polymer-doped being controlled better.Particularly, nanotube-ceramic complexes of describing now can help to realize the required dispersion of SWNTS in the used polymer substrate of this type equipment.

And the cost advantage of this composition has advantage economically when making it be used for solar cell.

Embodiment

The applicant studies, and the required nanotube diameter of performance optimization distributes and quantity in nanotube-ceramic complexes reflecting device on the scene to determine to make.

The SWNTS of high temperature preparation has demonstrated wideer diameter and has distributed, and center of distribution is positioned at the major diameter place, but bunch size little [2].

The H that in the carbon source that is adding reactor, adds small concentration ₂The time, diameter takes place similarly to increase.But, if H ₂Concentration is too high, begins to form carbon nano-fiber, and the present invention has lost the selectivity to SWNTS.Made the SWNTS (0.8nmOD) of minor diameter when for example, adopting pure CO; In CO, contain 3%H ₂The time, diameter increases (1.3nm OD); In CO, contain 10%H ₂The time, that generate under the situation mostly is many walls nanotube (19nm OD).

Simultaneously, studied the field reflectivity properties of this series of samples, to determine that the SWNTS diameter distributes and the influence of SWNTS quality of materials.Fig. 4 shows the I of relevant nanometer pipe-ceramic complexes of these three samples and the relation curve of V.In order to obtain the optimum performance of a transmitter, obviously need under low electric field, have high current density.After remembeing this notion, the composite with optimum performance is at 850 ℃ and 3%H ₂The time obtain just become apparent.There is not H at 850 ℃ ₂The poor-performing of the sample of time preparation, the poorest at the sample performance of 750 ℃ of preparations.

In all cases, sample has demonstrated good stable, this means to reach almost 5mA/cm ²Current density after sample almost do not occur aging.This can observe by hysteresis low in I and the V relation curve.

The applicant has also studied the influence of dielectric structure to the field emission emission characteristic of nanotube-ceramic complexes.For this reason, prepared a series of different composites, adopted the carrier of different silica as catalyst granules.Silica comprises that average pore diameter is

Silica gel 60, not having micro-pore and surface area is 250m ²The Hi-of/g

-210 silica, and two kinds of specific areas are respectively 90 and 380m ²/ g and average grain diameter be respectively 20 with the different aerosols of 7nm (

90 Hes

380).In addition, synthesize a series of MCM-41 especially, attempted to improve an emission.Because this material demonstrates the air hole structure of high-sequential and to the low selectivity of SWNTS, so this composite causes field emission performance poorer in course of reaction.

Mix the CTAOH of 100g and the tetramethyl silicic acid ammonium of 50g, and stirred 30 minutes, preparation MCM-41 silica.The Hi-that in solution, adds 12.5g then

-x stirred 5 minutes, imported in the autoclave.Reactor places 150 ℃ baking oven 48 hours.After reactor takes out, cool to room temperature.Solid carries out vacuum filtration with the Buchner funnel, cleans with nanometer pure (nanopure) water, and dry under environmental condition.Pre-dried solid is heated to 540 ℃ from room temperature and calcines in air, described intensification surpasses 24 hours, is incubated 2 hours then.Sample after the calcining is designated as MCM-41-210, MCM-41-233 and MCM-41-915, shows that parent material is different Hi-

Silica.Fig. 5 has provided the TEM photo of synthetic MCM.Photo has shown the regular hexagonal array of even raceway groove, and this is the typical pattern of MCM-41.The average pore size of all samples is approximately

We also adopt X-ray diffraction spectrum (XRD) that the MCM sample is characterized.XRD figure spectrum (Fig. 6) shows that sample has shown the hexgonal structure that attach structure is orderly, because all collection of illustrative plates have three interplanar distances (hk1) feature relevant with hexagonal lattice structure.Peak in the collection of illustrative plates is narrow peak (100), gets very and open (110) and (200) reflection peak.Pillar cell cell parameter (a ₀) be equivalent to interplanar distance d100, hexagonal cell parameter (a ₀) be equivalent to interplanar distance d ₁₀₀(2/ √ 3).The hole diameter of determining sample from interplanar distance is about

This and TEM data are coincide finely.

In order to study the structure of carrier, adopt different carriers to prepare identical Co: the Mo catalyst, and under 850 ℃ of reaction conditions, prepared nanotube-ceramic complexes.In this case, there is not hydrogen in the charging.Fig. 7 has provided the I and the V relation curve of these samples.In this case, the sample with best field emission performance is to have

Those of silica, described silica are the fumed silicas that average grain diameter is positioned at the nanoscale scope. 90 samples ratio

380 performance is quite a lot of slightly, and average grain diameter is 20nm, and

380 average grain diameter is 7nm.As if the nuance of field between the emission characteristic of these two samples shows with the general structure of carrier and compares, and it is far short of what is expected that fumed silica is generally the average grain diameter importance of 7-20nm.By Hi-

The sample of-210 silica preparations and

380 samples are compared, and in order to obtain same current density (4.76mA/cm2), need to increase the electric field (4.02V/ μ m is to 2.41V/ μ m) of 1.6V/ μ m.In the case, the structure of silica is different fully, because Hi-

-210 silica are that specific area is 150m ²The precipitated silica of/g.Hi-

A key property of-210 is not have micro-pore.On the other hand, silica gel 60 is highly micro-poreizations.Adopt the nanotube-ceramic complexes of this silica preparation, have poor field emission performance, can not obtain greater than 0.12mA/cm ²Current density.Equally, the hole diameter of preparation is

The MCM of grade has demonstrated same poor behavior.As if it is low to the selectivity of SWNTS that the low quality parameter (1-D/G) that is gone out by raman spectroscopy measurement is judged these samples, and this is exactly the reason of this phenomenon.

Composite has demonstrated excellent performance, has obtained target current density under extremely low electric field.Adopt Hi-in order to verify

The uniformity of field emission and above-mentioned synthesis temperature has prepared another kind during-210 silica Composite, nanotube-ceramic complexes is synthetic at 750 ℃.Fig. 8 has provided and at the comparative result of 850 ℃ of preparations.Observed same trend (synthesis temperature is high more, and performance is good more) once more.Composite 850 ℃ of preparations is well more a lot of than the performance 750 ℃ of preparations.

To synthetic at 850 ℃

What composite need be mentioned is observed extremely low hysteresis in its I and V relation curve on the other hand.Ce Shi other material does not all show this performance herein, is reaching almost 5mA/cm ²Current density after sample almost not aging.

At last, studied in the SWNTS composite carbon content to the influence of material field transmitting property.In order to reach this purpose, adopted distinct methods to change carbon/silica ratio.First method is the carbon productive rate that improves in the SWNTS of synthesis of nano pipe-ceramic complexes.By the metal load of original catalyst particle is brought up to 6% from 2%, realized this target.Adopt this method, compare two kinds of composites, a kind of SWNTS of 10% that contains, another kind contains 20%SWNTS.Though studies show that in early days and adopt the mixture of 50%SWNTS/50% dielectric material to obtain optimal performance, the I of these two samples and V relation curve (Fig. 9) show that the material that contains 16%SWNTS is poorer than the material property that only contains 10%SWNTS.Productive rate does not increase with the tenor of catalyst is linear, thus the metal decrease in efficiency, as shown in Table II.For example, for two samples that contain 2wt% and 10wt% metal, metal efficient is respectively 500wt% and 200wt%.Though even efficient is also very low under the best circumstances, every mole of active specy Co has prepared only 147 moles of carbon, and the efficiency far that adopts synthetic method of the present invention to obtain is higher than the efficient that any other method obtains.For example, Ci etc. report [23], and adopting floating catalytic agent method, acetylene is that every mole of Fe obtains 3.25mol carbon as carbon source and Fe action activity catalyst gained peak efficiency.Equally, The C/Fe ratio is 10/1[24 in the method].

Table II has also provided Raman spectrum (514nm laser) the gained mass parameter x (1-D/G) by different catalysts (the metal load is 2wt%, 6wt% and 10wt%) products therefrom.Though the trend that mass parameter reduces along with the increase of metal load is conspicuous, it should be noted that quality difference in this metal loading range of SWNTS is little, should not become the reason of an emission differences.

Table II-Co: Mo (1: 3)/SiO ₂-Hi-

In the series catalyst, the relation between mass parameter 1-D/G, carbon productive rate and metal efficient and the metal load.Be reflected under 750 ℃ and the 5.8atm and carry out.

Generally speaking, the increase of metal/SWNTS ratio causes field emission performance to descend, so preferred nanotube-ceramic complexes is only to contain 10%SWNTS but the SWNTS/ metal is more the sort of than maximum.

Though adopt the important cost advantage is arranged, studied other and be used for improving the post processing of SWNTS content as nanotube-ceramic complexes (not having purifying) shown in the present.Post processing is made up of following: remove metal with dense HCL acid etching, partly remove silica supports with NaOH solution alkaline etching and HF solution acid etching.

The sample that NaOH handles brings up to 80% with SWNTS concentration, but product does not have a reflection fully.Sample with the HF purifying is even lower silica volume, causes material to have only the silica of trace.Material is two kinds of multi-form measurements down.The first, the gel form that mainly contains 1%SWNTS and 99% water that forms by purification process, the secondth, the dried forms that the gel freeze-drying forms.Figure 10 has provided these with I and V relation curve form and has had the comparative result of the new sample of nanotube-ceramic complexes.Same these purification process do not make the field emission of nanotube that any improvement takes place, and but certain degree ground has reduced material property.At last, best field emmision material is still and contains 10%SWNTS ground nanotube-ceramic complexes.

Under the condition of the scope of the invention that does not depart from back claim qualification, can change the structure and the operation of described various parts, element and assembling, perhaps change the step or the order of steps of described method.

Citing document

1.″Method?of?Producing?Nanotubes ¹¹?D.E.Resasco，B.Kitiyanan，J.H.Harwell.W.Alvarez.U.S.PatentNo.6,333,016(2001).″Method?and?Apparatus?for?ProducingNanotubes″D.E?Resasco.L.Baizano.W.Alvarez.B.Kitlyanan，US?Patent?6，4，3，487(2002)

2.″Characterization?of?single-walled?carbonnanotubes(SWNTS)produced?by?CO?disproportionation?onCo-Mo?catalysts″W.E.Alvarez，F.Pompeo.J.E.Herrera，L.Balzano.and?D.E.Resasco.Chemistiy?of?Materials?14(2002)1853-1858

3.“Synergism?of?Co?and?Mo?in?the?catalytic?productionof?single-wall?carbon?nanotubes?by?decomposition?of?CO″W.E.Alvarez，B.Kitlyanan.A.Borgna.and?D.E.Resasco，Carbon，39(2001)547-558

4.“Relationship?Between?the?Structure/Compositionof?Co-Mo?Catalysts?and?their?Ability?to?Produce?Single-Walled?Carbon?Nanotubes?by?CO?Disproportionation″Jose?E.Herrera，Leandro?Balzano，Armando?Borgna，WalterE.Alvarez，Daniel?E.Resasco，JournalofCatalysis?204(2001)129

5.″Large?screen?home?FEDs?for?advanced?digitalbroadcasting″，F.Sato?and?M.Seki，Proc.ofAsiaDisp/ay/IDW′01，Nagoya，Japan?(2001)1153

6.″New?CNT?Composites?for?FEDs?That?Do?Not?RequireActivation″D.S.Mao，R.L.Fink，G.Monty，L.Thuesen，andZ.Yaniv，Proc.9th?1nL?Display?Workshops?IIDW′02，Hiroshima，Japan?(2002)1415

7.″Transmittance?and?mechanical?properties?ofPMMA-fumed?silicas?composites″B.Abram?off，J.Covino，JAppi.Poly.Sci.46(1959)

8.″Study?of?the?effect?of?the?effect?of?fumed?silicaon?rigid?PVC?properties″S.Fellahi，S.Boukobbal，F.Boudjenana，J?Vinyl.Tech.15(1993)17-21

9.″Influence?of?fumed?silica?properties?on?theprocessing，curing?and?reinforcement?properties?ofsilicone?rubber″HCochrane，C.S.Lin，Rubber?Chem.Technol.66(1993)48-60

10.″Rheological?and?mechanical?properties?of?filledrubber：silica-silicone″M.I.Aranguren，E.Mora，C.W.Macosko，J.Saam，Rubber?Chem.Technol.67(1994)820-33

11.″Compounding?fumed?silicas?intopolydimethylsiloxane：bound?rubber?and?final?aggregatesize″M.I.Aranguren，E.Mora，C.W.Macosko，J.Saam，J.Colloid?Interface?Sci..195(1997)329-37

12.″Effect?of?polymer-filler?and?filler-fillerinteractions?on?dynamic?properties?of?filledvulcanizates″M.J.Wang，Rubber?Che.TechnoL?71(1998)520-89

13.″Dental?material?with?inorganic?filler?particlescoated?with?polymerizable?binder″H.Rentsch，W.Mackert，Eur.PaL?AppL，EP?732099?A2?19960918(1996)

14.″Thermal?conductivity，elastic?modulus，andcoefficient?of?thermal?expansion?of?polymer?compositesfilled?with?ceramic?particles?for?electronic?packaging.″C.P..Wong，Bollampally，S.Raja，J.Appi.Polym.Sci.74(1999)3396-403

15.″Role?of?rheological?additives?in?protectivecoatings″R.E.Van?Dorem，D.N.Nash，A.Smith，J.Protective?Coatings?Linings?6(1989)47-52

16.″SWNT-filled?thermoplastic?and?elastomericcomposites?prepared?by?miniemulsion?polymerization″H.Barraza，F.Pompeo，E.O′Rear，D.E.Resasco，NanoLetters2(2002)797-802

17.″Nucleation?of?Polypropylene?Crystallization?bySingle-Walled?Carbon?Nanotubes″，B.P.Grady，F.Pompeo，R.L.Shambaugh，and?D.E.Resasco，Journal?of?PhysicalChemistry?B?106(2002)5852-5858

A.Razavi，Chemistry?3(2000)615

18.″The?influence?of?Cr?precursors?in?the?ethylenepolymerization?on?Cr/SiO ₂?catalysts″，A.B.Gaspar，L.C.Dieguez，Applied?Catalysis?A：General?227(2002)241-254

19.″Graphite?Nanofibers?as?an?Electrode?for?Fuel?CellApplications″，Bessel，Carol?A.；Laubernds，Kate；Rodriguez，Nelly?M.；Baker，R.Terry?K.，J?Phys.Cliem.B(2001)，105，1089-5647

20.“Pt-W03supported?on?carbon?nanotubes?as?possibleanodes?for?direct?methanol?fuel?cells″，B.Rajesha，V.karthik，S.Karthikeyan，K.Ravindranathan?Thampi，J.-M.Bonard，B.Viswanathan?Fuel?81(2002)2177-2190

21.″Single-wall?carbon?nanotube/conjugated?polymerphotovoltaic?devices″，Kymakis，E.，Amaratunga，G.A.J.，Applied?Physics?Letters?(2002)，80(1)，112-114

22.Ci?L.，Xie?S.，Tang?D.，Yan?X.，Li?Y.，Liu?Z.，ZouX.，Zhou?W.，Wang?G.，Chem.Phys.Lett.，349(3，4)(2001)191

23.Nikolaev?P.，Bronikowaki?M.J.，Bradley?R.k.，Rohmund?F.，Colbert?D.T.，Smith?KA.，Smalley?R.E.，Chem.Phys.Lett.，313(1999)91

24.Laurence，R.L.，and?M.G.Chiovetta，″Heat?and?MassTransfer?During?Olefin?Polymerization?from?the?Gas?Phase，″Polymer?Reaction?Engineering：Influence?of?ReactionEngineering?on?Polymer?Properties，k.H.Reichert?and?W.Geisler，eds.，Hanser，Munich(1983)

Claims

1. carbon nano tube-polymer composition comprises:

Carbon nanotube-ceramic composites, it comprises:

Metal catalyst particles comprises:

At least one of Co, Ni, Ru, Rh, Pd, Ir, Pt, at least a VIb family metal, and carrier material combine the formation particle form; With

Be deposited on the carbon product on the catalyst granules, wherein at least 80% described carbon product comprises SWCN;

With

Polymer, wherein said carbon nanotube-ceramic composites combines with described polymer, forms the carbon nano tube-polymer composition.

2. the carbon nano tube-polymer composition of claim 1, wherein said at least a VIb family metal is selected from Cr, Mo or W.

3. the carbon nano tube-polymer composition of claim 1, the carrier material of the catalyst granules of wherein said carbon nanotube-ceramic composites is selected from silica, aluminium oxide, MgO, ZrO ₂And zeolite.

4. the carbon nano tube-polymer composition of claim 1, wherein catalyst granules comprises Co and Mo.

5. the carbon nano tube-polymer composition of claim 1, wherein said catalyst granules comprises Co and the Mo that is placed on the silica that does not have micropore.

6. the carbon nano tube-polymer composition of claim 1, wherein said catalyst granules comprises the metal of 0.1 weight %-20 weight %.

7. the carbon nano tube-polymer composition of claim 1, wherein the carbon product of at least 90% described carbon nanotube-ceramic composites is a SWCN.

8. the carbon nano tube-polymer composition of claim 1, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

9. the carbon nano tube-polymer composition of claim 1, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

10. the carbon nano tube-polymer composition of claim 1, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

11. the carbon nano tube-polymer composition of claim 1, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

12. the carbon nano tube-polymer composition of claim 1, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

13. the carbon nano tube-polymer composition of claim 1, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

14. the carbon nano tube-polymer composition of claim 1, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

15. the carbon nano tube-polymer composition of claim 1, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

16. the carbon nano tube-polymer composition of claim 1, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

17. the carbon nano tube-polymer composition of claim 1, wherein carrier material is a silica.

18. the carbon nano tube-polymer composition of claim 1, wherein carrier material is the silica that does not have micropore.

19. the carbon nano tube-polymer composition of claim 1, wherein carrier material is a fumed silica.

20. a ceramic composite comprises:

Carbon nanotube-ceramic composites, it comprises:

Metal catalyst particles comprises:

With

Ceramic substrate, wherein said carbon nanotube-ceramic composites combines with described ceramic substrate, forms the carbon nano tube-polymer composition.

21. the ceramic composite of claim 20, wherein said at least a VIb family

Metal is selected from Cr, Mo or W.

22. the ceramic composite of claim 20, the carrier material of the catalyst granules of wherein said carbon nanotube-ceramic composites is selected from silica, aluminium oxide, MgO, ZrO ₂And zeolite.

23. the ceramic composite of claim 20, wherein catalyst granules comprises Co and Mo.

24. the ceramic composite of claim 20, wherein said catalyst granules comprise Co and the Mo that is placed on the silica that does not have micropore.

25. the ceramic composite of claim 20, wherein said catalyst granules comprise the metal of 0.1 weight %-20 weight %.

26. the ceramic composite of claim 20, wherein the carbon product of at least 90% described carbon nanotube-ceramic composites is a SWCN.

27. the ceramic composite of claim 20, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

28. the ceramic composite of claim 20, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

29. the ceramic composite of claim 20, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

30. the ceramic composite of claim 20, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

31. the ceramic composite of claim 20, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

32. the ceramic composite of claim 20, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

33. the ceramic composite of claim 20, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

34. the ceramic composite of claim 20, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

35. the ceramic composite of claim 20, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

36. the ceramic composite of claim 20, wherein carrier material is a silica.

37. the ceramic composite of claim 20, wherein carrier material is the silica that does not have micropore.

38. the ceramic composite of claim 20, wherein carrier material is a fumed silica.

39. a CNT field transmitter comprises:

Carbon nanotube-ceramic composites, it comprises:

Metal catalyst particles, it comprises: one of Co, Ni, Ru, Rh, Pd, Ir, Pt at least, at least a VIb family metal, and carrier material combine the formation particle form; With

Wherein said carbon nanotube-ceramic composites combines and sticks to binding agent on the electrode surface, forms described transmitter.

40. the CNT field transmitter of claim 39, wherein said at least a VIb family metal is selected from Cr, Mo or W.

41. the CNT field transmitter of claim 39, the carrier material of the catalyst granules of wherein said carbon nanotube-ceramic composites is selected from silica, aluminium oxide, MgO, ZrO ₂And zeolite.

42. the CNT field transmitter of claim 39, wherein the catalyst granules of carbon nanotube-ceramic composites comprises Co and Mo.

43. the CNT field transmitter of claim 39, wherein said catalyst granules comprises Co and the Mo that is placed on the silica that does not have micropore.

44. the CNT field transmitter of claim 39, wherein said catalyst granules comprise the metal of 0.1 weight %-20 weight %.

45. the CNT field transmitter of claim 39, wherein the carbon product of at least 90% described carbon nanotube-ceramic composites is a SWCN.

46. the CNT field transmitter of claim 39, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

47. the CNT field transmitter of claim 39, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

48. the CNT field transmitter of claim 39, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

49. the CNT field transmitter of claim 39, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

50. the CNT field transmitter of claim 39, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

51. the CNT field transmitter of claim 39, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

52. the CNT field transmitter of claim 39, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

53. the CNT field transmitter of claim 39, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

54. the CNT field transmitter of claim 39, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

55. the CNT field transmitter of claim 39, wherein carrier material is a silica.

56. the CNT field transmitter of claim 39, wherein carrier material is the silica that does not have micropore.

57. the CNT field transmitter of claim 39, wherein carrier material is a fumed silica.

58. a CNT fuel cell electrode comprises:

Carbon nanotube-ceramic composites, it comprises:

Wherein said carbon nanotube-ceramic composites combines with eelctro-catalyst and ionomer and forms fuel cell electrode.

59. the CNT fuel cell electrode of claim 58, wherein said at least a VIb family metal is selected from Cr, Mo or W.

60. the CNT fuel cell electrode of claim 58, the carrier material of the catalyst granules of wherein said carbon nanotube-ceramic composites is selected from silica, aluminium oxide, MgO, ZrO ₂And zeolite.

61. the CNT fuel cell electrode of claim 58, wherein the catalyst granules of carbon nanotube-ceramic composites comprises Co and Mo.

62. the CNT fuel cell electrode of claim 58, wherein said catalyst granules comprise Co and the Mo that is placed on the silica that does not have micropore.

63. the CNT fuel cell electrode of claim 58, wherein said catalyst granules comprise the metal of 0.1 weight %-20 weight %.

64. the CNT fuel cell electrode of claim 58, wherein the carbon product of at least 90% described carbon nanotube-ceramic composites is a SWCN.

65. the CNT fuel cell electrode of claim 58, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

66. the CNT fuel cell electrode of claim 58, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

67. the CNT fuel cell electrode of claim 58, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 0.7nm-1.0nm.

68. the CNT fuel cell electrode of claim 58, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

69. the CNT fuel cell electrode of claim 58, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

70. the CNT fuel cell electrode of claim 58, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 1.0nm-1.2nm.

71. the CNT fuel cell electrode of claim 58, wherein the external diameter of the SWCN of at least 50% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

72. the CNT fuel cell electrode of claim 58, wherein the external diameter of the SWCN of at least 70% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

73. the CNT fuel cell electrode of claim 58, wherein the external diameter of the SWCN of at least 90% carbon nanotube-ceramic composites is 1.2nm-1.8nm.

74. the CNT fuel cell electrode of claim 58, wherein carrier material is a silica.

75. the CNT fuel cell electrode of claim 58, wherein carrier material is the silica that does not have micropore.

76. the CNT fuel cell electrode of claim 58, wherein carrier material is a fumed silica.