CN101282905A - Carbon nanostructures manufactured from catalytic templating nanoparticles - Google Patents
Carbon nanostructures manufactured from catalytic templating nanoparticles Download PDFInfo
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- CN101282905A CN101282905A CNA2006800373227A CN200680037322A CN101282905A CN 101282905 A CN101282905 A CN 101282905A CN A2006800373227 A CNA2006800373227 A CN A2006800373227A CN 200680037322 A CN200680037322 A CN 200680037322A CN 101282905 A CN101282905 A CN 101282905A
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Abstract
Methods for manufacturing carbon nanostractures include: 1) forming a plurality of catalytic templating particles using a plurality of dispersing agent molecules; 2) forming an intermediate carbon nanostructure by polymerizing a carbon precursor in the presence of the plurality of templating nanoparticles; 3) carbonizing the intermediate carbon nanostructure to form a composite nanostructure; and 4) removing the templating nanoparticles from the composite nanostructure to yield the carbon nanostructures. The carbon nanostructures are well-suited for use as a catalyst support. The carbon nanostructures exhibit high surface area, high porosity, and high graphitization. Carbon nanostructures according to the invention can be used as a substitute for more expensive and likely more fragile carbon nanotubes.
Description
Background of invention
1. invention field
The present invention relates generally to carbon nanomaterial.More specifically, the present invention relates to use the carbon nano-structured of carbon precursor and catalytic templating particle (catalytic templating particle) preparation.
2. correlation technique
Carbon material is used for many fields as high-performance and functional materials.As everyone knows, the organic compound pyrolysis is the most frequently used method for preparing carbon material.For example, can be by producing carbon material in the temperature pyrolysis Resorcinol-formaldehyde gel that surpasses 600 ℃.
Unbodied often by most of carbon material that pyrolysis organic compound under 600-1400 ℃ temperature obtains, perhaps have unordered structure.It is very favorable obtaining carbon material highly crystalline or graphite-like, because graphite shows unique character.For example, graphite material has electroconductibility, forms unique nano material, for example carbon nanotube.But, use existing method to be difficult to prepare the graphite-structure of these well-crystallized by pyrolysis (particularly carrying out pyrolysis) in the temperature that is lower than 2000 ℃.
In order to obtain graphite-structure in lower temperature, people have carried out many researchs to carrying out aspect the carbonization in the presence of metal catalyst.Described catalyzer normally with the salt of carbon precursor blended iron, nickel or cobalt.Use catalyzed graphitization, can prepare graphite material in the temperature between 600 ℃ to 1400 ℃.Most of catalyzed graphitization method concentrates on the preparation graphite nanotubes.But, the productive rate of crystalline material still very low (for example, for carbon nanotube, productive rate is less than 2%).These low-yield make and are difficult to use described nano material to make useful product.
Summary of the invention
The present invention relates to use carbon precursor and the carbon nano-structured novel method of Preparation of Catalyst.Around a plurality of template nano particles, form carbon nano-structured.In an illustrative embodiments, use organic dispersing agent to prepare the template nano particle by catalytic metal atom.The catalytic nanometer particle both can be used as the catalyzer in carbonization of carbon precursor and/or the polymerization process again valuably as forming carbon nano-structured nucleation site.
Comprise whole following steps or a part wherein according to the carbon nano-structured novel method of preparation of the present invention:
(i) form a plurality of catalytic templating nano particles by following steps:
(a) make a plurality of precursor catalyst atoms and a plurality of organic dispersing agent molecular reaction, form the catalyst atoms of complexing;
(b) appoint the catalyst atoms of complexing or make the catalyst atoms of complexing form the template nano particle;
(ii) carbon nano-structured by in the presence of the template nano particle, making carbon precursor polymerization reaction take place form one or more intermediates;
(iii) make the carbon nano-structured carbonization of intermediate, form a plurality of composite nanostructures; With
(iv) from composite nanostructure, remove the template nano particle, obtain carbon nano-structured.
In the method for the invention, use dispersion agent to form dispersive template nano particle.Dispersion agent be comprise one or more can with the organic molecule of catalyst atoms bonded functional group.One preferred embodiment in, described one or more functional groups comprise hydroxyl, carboxyl, carbonyl, amine, acid amides, nitrile, the nitrogen with free lone-pair electron, amino acid, mercaptan, sulfonic acid, sulfonic acid halide, carboxylic acid halides or their arbitrary combination.Described dispersant molecule combines with catalyst atoms, forms complex compound.Make the catalyst atoms reaction of complexing then or reunite formation solid (solid) catalytic templating particle.Formation, granularity and/or the dispersion of organic dispersing agent may command catalytic templating nano particle.
In the method for the invention, the catalytic templating nano particle is as the template of preparation nanostructure.When the template nano particle mixed with the carbon precursor, the template nano particle provided carbonization and/or polyreaction to begin or enhanced nucleation site.Because the template nano particle is formed by catalyzing atom,, be suitable as the catalyzer of carbonization and/or polyreaction again so template particles both had been suitable as the nucleation site.This feature of the present invention has been eliminated the needs that add template particles and catalyzer (for example silica gel and metal-salt) respectively.In this method, the solid catalysis template particles has avoided the catalyst atoms of independent adding to become the rough sledding in nucleation site.Catalytic templating nano particle of the present invention can advantageously produce than what use existing method preparation carbon nano-structuredly has the carbon nano-structured of the character of homogeneous (for example inner aperture) more.
In an exemplary embodiment, it is carbon nano-structured that method of the present invention produces annular.This annular can make the carbon nano-structured useful character that has, for example high porosity and high surface area.Suchlike these beneficial properties make the carbon nano-structured solid support material that can be used as fuel-cell catalyst.High surface area provides high content of metal, and high porosity has improved the performance of fuel-cell catalyst owing to the diffusion that has improved reactant.Their high conductivity makes nanostructure can be used for the male or female of fuel cell.The carbon nano-structured carbon nanotube that can replace usually more expensive and easier fragmentation.
Can more fully understand these and other advantage of the present invention and feature from the following description and the appended claims.
Brief Description Of Drawings
In order further to set forth above-mentioned and other advantage and feature of the present invention, the present invention is more specifically described by the embodiment of middle explanation with reference to the following drawings.Should be understood that these accompanying drawings have only described exemplary embodiment of the present invention, therefore should not think to limit the scope of the invention.By using the following drawings concrete especially and describe and explain the present invention in detail:
Figure 1A is a plurality of carbon nano-structured high resolution TEM image that forms according to an exemplary embodiment of the present invention;
Figure 1B is the high resolution TEM image of each carbon nano-structured feature details (close-up) of expression Figure 1A;
Fig. 1 C is the high resolution TEM image of the carbon nano-structured close-up images (closer image) of expression Figure 1A;
Fig. 2 A is a plurality of carbon nano-structured high resolution TEM image that forms according to an exemplary embodiment of the present invention;
Fig. 2 B is the high resolution TEM image of each carbon nano-structured close-up images of presentation graphs 2A;
Fig. 3 A is a plurality of carbon nano-structured high resolution TEM image that forms according to an exemplary embodiment of the present invention;
Fig. 3 B is the high resolution TEM image of each carbon nano-structured close-up images of presentation graphs 3A;
Fig. 4 A is the carbon nano-structured high resolution SEM image that forms according to an exemplary embodiment of the present invention, shows that their shape is similar to sphere;
Fig. 4 B is the high resolution SEM image that shows each carbon nano-structured close-up images of Fig. 4 A.
The detailed description of illustrative embodiments
I. foreword and definition
The present invention relates to prepare carbon nano-structured method and this is carbon nano-structured as the support of the catalyst application of (for example being used for fuel-cell catalyst).Preparing carbon nano-structured method generally comprises: 1) by making the reaction of catalyst atoms and organic dispersing agent form a plurality of solid catalysis template particles; 2) carbon nano-structured by in the presence of described template nano particle, making the carbon precursor polymeric form intermediate; 3) to carbon nano-structured carbonization, the formation composite nanostructure of carrying out of intermediate; With 4) from composite nanostructure, remove the template nano particle, stay carbon nano-structured.That uses the above-mentioned steps preparation carbon nano-structuredly has one or more carbon-coatings, these carbon-coatings form wall, as if the tubular structure that defines carbon nano ring or go to push up from these walls of TEM image, but during in conjunction with the SEM image analysis TEM image of same material, the feature of these nanostructures is hollow, and is irregular many squashes shape (or globoid).In one embodiment, see the botryoidal clustering architecture of carbon nano-structured formation from the SEM image, but the TEM pictorial display of same material this carbon nano-structured be hollow many walls nanostructure.
For the present invention, the precursor catalystic material is any material that can obviously improve carbon precursor carbonization speed when using with the carbon combination of precursors.The non-limitative example of precursor catalystic material comprises iron, cobalt and/or nickel.
The solid catalyst template particles is that all basically template particles all are the particles of being made by one or more catalytic materials.
II. be used to prepare carbon nano-structured component
Following exemplary compositions can be used for carrying out according to the carbon nano-structured above-mentioned steps of preparation of the present invention.
A. polymerisable carbon precursor
The carbon material of any kind all can be used as carbon precursor of the present invention, as long as this carbon material can disperse template particles, polymerization to form the intermediate nanostructure and be carbonized by thermal treatment.Suitable compound comprises monocycle and polynuclear aromatic compound, for example has the benzene and the naphthalene derivatives of polymerizable functional group.Can form the cyclic cpds of monocycle and polynuclear aromatic compound when also being included in heating.The functional group that can participate in polyreaction comprises COOH, C=O, OH, C=C, SO
3, NH
2, SOH, N=C=O etc.
Polymerizable carbon precursor can be independent one type molecule (for example, but the compound of self-polymerization), and perhaps polymerizable carbon precursor is two or more different combination of compounds of copolymerization together.For example, in an illustrative embodiments, the carbon precursor can be Resorcinol-formaldehyde gel.In this pair of compound embodiment, formaldehyde by and the hydroxyl polymerization reaction take place of Resorcinol molecule be used as linking agent between the Resorcinol molecule.
Other example of suitable polymerizable precursors material comprises Resorcinol, phenol resins, melamine-formaldehyde gel, poly-(furfuryl alcohol), poly-(vinyl cyanide), sucrose, petroleum pitch etc.Other polymerisable benzene, quinone and similar compounds also can be used as the carbon precursor, and are well known by persons skilled in the art.
In an illustrative embodiments, but the carbon precursor is a hydrothermal solution polymeric organic compound.This suitable class organic compound comprises citric acid, vinylformic acid, phenylformic acid, acrylate, divinyl, vinylbenzene, styracin etc.
B. catalytic templating nano particle
As described below, form the catalytic templating particle and generally comprise following steps: make a plurality of template catalyst atoms and a plurality of dispersant molecule reaction in solvent, form the catalyst atoms of complexing.The catalyst atoms of described complexing reaction then forms nano particle.
1. carbon precursor catalyst atoms
The precursor catalyst atoms can be anyly can cause or promote carbonization of carbon precursor and/or polymeric material.One preferred embodiment in, this catalyzer is a transition-metal catalyst, includes but not limited to iron, cobalt or nickel.These transition-metal catalysts are particularly suitable for many polymerization and/or the carburizing reagents that relate to above-mentioned carbon precursor of catalysis.
2. dispersion agent
Except catalyst atoms, catalyst complex of the present invention comprises one or more dispersion agents.Described dispersion agent is selected, formed to promote nanocatalyst particulate with required stability, granularity and/or homogeneity.Dispersion agent in the scope of the invention comprises various little organic molecules, polymkeric substance and oligopolymer.This dispersion agent can or be dispersed in suitable solvent or the catalyst atoms in the carrier with dissolving and interact and combine, these interactions and combination can be finished by various mechanism, comprise ionic linkage, covalent linkage, Van der Waals force interaction/combination, lone-pair electron combination or hydrogen bond.
For the combination between dispersion agent and the catalyst atoms is provided, dispersion agent comprises one or more suitable functional groups.Preferred dispersing agent comprises and has and can or have the functional group of the key (for example hydrogen bond) that can form other type with electric charge or one or more lone-pair electron of metal catalyst atoms complexing.These functional groups make and form strong binding interactions between dispersion agent and the catalyst atoms.
Dispersion agent can be natural or synthetic compound.In catalyst atoms is that metal, dispersion agent are in the situation of organic compound, and the catalyst complex of formation can be an organometallic complex.
In an illustrative embodiments, the functional group of dispersion agent comprises one or more following groups that are selected from: hydroxyl, carboxyl, carbonyl, amine, acid amides, nitrile, the nitrogen with free lone-pair electron, amino acid, mercaptan, sulfonic acid, sulfonic acid halide or carboxylic acid halides.Described dispersion agent can be simple function, difunctionality or polyfunctional.
The example of suitable simple function dispersion agent comprises alcohol of ethanol and propyl alcohol and so on and the carboxylic acid of formic acid and acetate and so on.Available difunctionality dispersion agent comprises: diprotic acid, for example oxalic acid, oxysuccinic acid, propanedioic acid, toxilic acid, Succinic Acid etc.; Glycol, for example ethylene glycol, propylene glycol, 1, ammediol etc.; Alcohol acid, for example oxyacetic acid, lactic acid etc.The multifunctional dispersion agent of available comprises sugar as glucose, polyfunctional carboxylic acids such as citric acid, pectin, Mierocrystalline cellulose etc.Other available dispersion agent comprises thanomin, mercaptoethanol, 2-mercaptoacetate, amino acid such as glycine, sulfonic acid such as sulfo group phenylcarbinol, sulfosalicylic acid, sulfo group beneze methane thiol and sulfo group benzene methanamine.Dispersion agent can also comprise the inorganic component component of silicon (for example based on).
Suitable polymers and oligopolymer in the scope of the invention comprise, but be not limited to polyacrylic ester, polyvinyl benzoate, poly-sulfuric acid vinyl ester, poly-sulfonic acid vinyl acetate (comprising sulfonated vinylbenzene), poly-carbonic acid bis-phenol ester, polybenzimidazole, polypyridine, sulfonated polyethylene terephthalate.Other suitable polymers comprises polyvinyl alcohol, polyoxyethylene glycol, polypropylene glycol etc.
Except the feature of dispersion agent, the mol ratio of dispersion agent and catalyst atoms also is favourable in the control catalyst suspension.More useful considerations is the mol ratio between dispersion agent functional group and the catalyst atoms.For example, in the situation of divalent-metal ion, need the monovalence functional group of two molar equivalents that theoretical chemistry metering ratio is provided.One preferred embodiment in, the mol ratio of dispersion agent functional group and catalyst atoms preferably is about 0.01: 1 to 100: 1, is more preferably 0.05: 1 to 50: 1, is most preferably 0.1: 1 to 20: 1.
Dispersion agent of the present invention can be used for forming the nano particle of very little and homogeneous.Usually, the nanocatalyst particulate granularity that forms in the presence of described dispersion agent is less than 1 micron.Preferred nano particle is more preferably less than 50 nanometers, most preferably less than 20 nanometers less than 100 nanometers.
In carbon precursor pyrolytic process, dispersion agent can suppress the reunion and the inactivation of granules of catalyst.The ability of this inhibition inactivation can improve the temperature of nanocatalyst work, and/or prolong the work-ing life of nanocatalyst under extreme pyrolytical condition.Only just catalytic activity has been kept several milliseconds more even comprise dispersion agent, perhaps even a few microsecond, but according to the kinetics of carbonization, this section period that the nanocatalyst life-span prolongs is particularly advantageous at high temperature.
3. solvent and other additive
The liquid medium for preparing the catalytic templating nano particle therein can comprise all kinds of SOLVENTS, comprises water and organic solvent.Solvent provides liquid medium to participate in during particle forms by the interaction to catalyst atoms and dispersion agent.In some cases, solvent can be used as less important dispersion agent, is used in combination with the main dispersion agent that is not used as solvent.In one embodiment, solvent also makes nano particle form suspension.Suitable solvent comprises water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, vinyl cyanide, acetone, tetrahydrofuran (THF), ethylene glycol, dimethyl formamide, methyl-sulphoxide, methylene dichloride etc., comprises their mixture.
Catalyst composition also comprises the granuloplastic additive of promotion nanocatalyst.For example, can add mineral acid and basic cpd, preferably add on a small quantity (for example, less than 5 weight %).The example of spendable mineral acid comprises hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid etc.The example of basic cpd comprises sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide and similar compounds.
Can also add solid material to promote the formation of nano particle.For example, in the catalyzer forming process, in solution, add ion exchange resin.Ion exchange resin can substitute above-mentioned acid or alkali.Use simple technology (for example centrifugal with filter) to be easy to solid material is separated from final iron catalyst solution or suspension.
III. prepare carbon nano-structured
Can use in the following steps all or part of to prepare of the present invention carbon nano-structured: (i) to form a plurality of dispersive catalytic templating nano particles by a plurality of precursor catalyst atoms and the reaction of a plurality of dispersant molecule; (ii) a plurality of catalytic templating nano particles (for example iron particle) are mixed with carbon precursor (for example citric acid), appoint the carbon precursor or make the carbon precursor polymeric, form a plurality of intermediate nanostructures; (iii) make the carbonization of intermediate nanostructure, form a plurality of composite nanostructures; (iv) from a plurality of composite nanostructures, remove the template nano particle, obtain carbon nano-structured.
A., the catalytic templating nano particle is provided
The method for preparing nano particle can be summarized as follows widely.At first, select the dispersion agent of precursor catalyst atoms He one or more types of one or more types.Secondly, make precursor catalyst atoms (for example ground state metal or metallic salt form) and dispersion agent (for example, carboxylic acid or its salt form) reaction or combination form catalyst complex.Catalyst complex is generally by at first being dissolved in catalyst atoms and dispersion agent in the suitable solvent, catalyst atoms being combined with dispersant molecule form.Various components can any order or array configuration make up or mix.In addition, a part of component can be before adding other component first premix, perhaps all combinations mix simultaneously.
In one aspect of the invention, can think that catalyst complex is the catalyst atoms and the dispersion agent of the complexing of solvent around having got rid of.In fact, scope of the present invention is included in and produces catalyst complex in the solution, removes then and desolvates, and obtains the exsiccant catalyst complex.The exsiccant catalyst complex can be rebuild by adding suitable solvent.
In an illustrative embodiments, the component blended time is about 1 hour to 14 days.This married operation carries out under 0 ℃-200 ℃ temperature usually.Preferred temperature is no more than 100 ℃.
The precursor catalyst atoms provides with the form of molysite usually, for example iron(ic) chloride, iron nitrate, ferric sulfate etc.These compounds dissolve in the water-based solvent usually.Using metal-salt to form the catalyst nano particle can be owing to anionic release forms other by product.If desired, can use metal-powder (for example iron) to avoid anionic formation.Usually, unique important by product is a hydrogen when using ferrous metal to prepare catalyzer, and they are overflowed in mixing process.Can effusion hydrogen or the material preparation granules of catalyst of other gas if use, then in preparation process usually with mixture termly (or continuously) ventilate and/or be exposed to air.
In an illustrative embodiments, after mixing step is finished or use when for example hydrogen further reduces, the nanocatalyst particle is an activity form.One preferred embodiment, the nanocatalyst particle forms as stable reactive metal nanocatalyst particulate suspension.Nanocatalyst particulate stability has prevented particle agglomeration together, makes them remain form of suspension.Even some or all nanocatalyst particle passage meetings in time settle down from solution, but can suspend once more at an easy rate by mixing these nanocatalyst particles.
Can add alkali (for example, strong aqua) the pH value of solution is adjusted between about 8-13, more preferably from about between the 10-11.Higher pH can be used for precipitating the precursor catalyst atoms of finely divided form.
The polymerization and/or the carburizing reagent of catalytic templating nano particle energy catalyzed carbon precursor.Being used for preparing catalytic templating particulate above-mentioned steps can promote catalyst atoms to be aligned to the particle with catalytic activity.On the contrary, the present inventor has been found that the reagent of buying on some markets (for example, at least a commercially available ironic citrate) does not have gratifying catalytic activity.
B. the polymerization of carbon precursor
, under polymeric condition around the template nano particle, catalytic templating nano particle and carbon precursor (for example, citric acid) are mixed at suitable carbon precursor.Because the template nano particle is a catalytic activity, the polymerization near the carbon precursor on template particles surface can preferentially be accelerated and/or cause to the template nano particle.
Usually the concentration of catalytic templating nano particle in the carbon precursor is selected,, still produced the nanostructure of shape homogeneous simultaneously farthest to increase the carbon nano-structured number that forms.Can be according to the type adjustment catalytic templating particulate amount of the carbon precursor that uses.In an illustrative embodiments, the mol ratio of carbon precursor and catalyst atoms is about 0.1: 1 to 100: 1, is more preferably 1: 1 to 30: 1.
Make precursor composition solidify adequate time, it is carbon nano-structured to form a plurality of intermediates like this around the template nano particle.Forming the intermediate required time of nanostructure depends on the type of the carbon precursor of the pH value of the type of temperature, catalystic material and concentration, solution and use.In polymerization process, intermediate is carbon nano-structured can be the aggregate (association) of organic structure or nanostructure independently, and the aggregate of these nanostructures is in carbonization and/or remove in the process of decolorizing carbon and divide.
Add for the ammonia of regulating the pH value and also can promote polyreaction by accelerating between polymeric speed and the increase precursor molecule crosslinked amount to take place.
But for hydrothermal solution polymeric carbon precursor, polyreaction is carried out under higher temperature usually.One preferred embodiment in, the carbon precursor is heated to about 0 ℃ to 200 ℃ temperature, more preferably be heated to about 25 ℃ to 120 ℃ temperature.
The example of the conditions suitable of the polyreaction of Resorcinol-formaldehyde gel (for example have the iron particle, the pH value of solution value is 1-14) is that solution temperature is 0 ℃ to 90 ℃, and be less than 1 hour to about 72 hours set time.Those skilled in the art determine to solidify the required condition of other carbon precursor easily under identical or different parameter.
In an exemplary embodiment, do not allow polyreaction proceed up to fully.Before the complete soln polymerization, stop solidification process and help to form a plurality of intermediate nanostructures, will obtain independently nanostructure, rather than the simple agglomerate of char-forming material (single mass).But the present invention includes following embodiment: it is carbon nano-structured that the carbon precursor forms a plurality of intermediates, and these intermediates are carbon nano-structured to interconnect or the part connection.In this embodiment, form independently nanostructure in carbonization and/or except that in the process of decolorizing carbon.
Forming intermediate by the dispersion of template nano particle, carbon nano-structured to cause forming a plurality of intermediates with unique shape and size carbon nano-structured.At last, the character of nanostructure depends on the shape and size that intermediate is carbon nano-structured at least in part.Have unique shape and size because intermediate is carbon nano-structured, so final nanostructure has favorable properties, for example high surface area and high porosity etc.
C. carbonization intermediate nanostructure
After obtaining the intermediate nanostructure, by heating, produce the composite nanostructure of carbonization immediately with they carbonizations.In an illustrative embodiments, the intermediate nanostructure is heated to about 500 ℃ to 2500 ℃ temperature.In this heat-processed, the intermediate nanostructure is perhaps otherwise left in the volatilization of the atom of oxygen and nitrogen and so on, and carbon atom rearranges or be coalescent, forms the carbon back structure.
One preferred embodiment in, this carburising step produces graphite based nanometer structure.The graphite based nanometer structure has with sp
2The carbon atom that the stratiform form of hydridization carbon atom is arranged.Graphite linings can provide uniqueness and favorable properties, for example electroconductibility and structural strength and/or rigidity.
D. it is carbon nano-structured to generate to remove template nano particle and/or decolorizing carbon
At last, from composite nanostructure, remove template nano particle and/or external amorphous (being non-graphite-like) carbon.Usually, use acid or alkali (for example nitric acid, hydrogen fluoride or sodium hydroxide) to remove the template nano particle.The method of removing template nano particle or decolorizing carbon depends on the type of template nano particle in the composite structure or catalyst atoms.Usually by being refluxed, composite nanostructure removed catalyst atoms or particle (for example, iron particle or atom) in about 3-6 hour in the 5.0M salpeter solution.
Can use any method to remove template nano particle and/or decolorizing carbon, as long as this process of removing can completely destroy carbon nanometer globoid and/or nano-rings structure.In some cases, it is useful removing some carbonaceous materials at least in part from the intermediate nanostructure in the process of removing.Also do not know at present in which time point formation cyclic shape of method, do not know it is in polymerization procedure, in the carburising step, or nano particle is removed in the step.
IV. carbon nano-structured
Method of the present invention is produced a kind of multi-wall carbon nano-tube structure, and this structure has useful properties, for example the shape of homogeneous, size and electrical properties.One preferred embodiment in, this is carbon nano-structured can be the orderly or unordered ring structure (being nano-rings or hollow many squashes shape or class globosity) with through hole.Of the present inventionly carbon nano-structuredly be specially adapted to some and need high porosity, high surface area and/or high-graphitized application.Carbon nano-structuredly can substitute common much expensive carbon nanotube according to what prepare described in the literary composition.
The size of nanostructure is to a great extent by the size decision that is used to prepare this carbon nano-structured template nano particle.Since carbon nano-structured formation around the template nano particle, the external diameter that therefore carbon nano-structured aperture or internal diameter are equivalent to the template nano particle usually.Carbon nano-structured internal diameter can be between about 0.5 nanometer to 90 nanometer.For some application (for example fuel cell), carbon nano-structured internal diameter is preferably between about 1 nanometer to 50 nanometer.
Figure 1A-1C, 2A-2B and 3A-3B have shown according to the exemplary carbon nano-structured TEM image of method preparation of the present invention, will describe in detail in following examples 1.Fig. 4 A-4B has shown according to the SEM image of the exemplary nano structure of the present invention's preparation, will describe in detail in following examples 1.
The TEM pictorial display of Figure 1A-1C, 2A-2B and 3A-3B general toroidal carbon nano-structured.The SEM pictorial display of Fig. 4 A-4B roughly spheric is carbon nano-structured.In TEM pictorial display many carbon nano-structured, external diameter is about 10 nanometer to 60 nanometers, and the aperture is about 10 nanometer to 40 nanometers.But, the present invention includes nanostructure with bigger and littler diameter.Usually, carbon nano-structured external diameter is less than about 100 nanometers, to keep the integrity of structure.
Thickness from the internal diameter of the wall of nanostructure to the outside diameter measuring wall of wall.By limiting the degree of above-mentioned carbon precursor polymeric and/or carbonization, can in preparation process, regulate the thickness of nanostructure.Usually, carbon nano-structured wall thickness is between about 1 nanometer to 20 nanometer.But, if desired, can prepare thicker and thinner wall.The advantage for preparing thicker wall is to obtain better structural integrity.The advantage for preparing thinner wall is to obtain higher surface-area and porosity.
Can also form carbon nano-structured wall by a plurality of graphite linings.The TEM image of Figure 1A, 1B and 1C has clearly illustrated a plurality of layers.In an illustrative embodiments, carbon nano-structuredly has about 2-100 graphite linings, more preferably about 5-50 graphite linings, the wall of 5-20 graphite linings more preferably from about.The number of graphite linings can change by regulating above-mentioned carbon nano-structured wall thickness.Carbon nano-structured graphite feature it is believed that can give the carbon nano-structured beneficial property (for example splendid electroconductibility) that is similar to multi-walled carbon nano-tubes.They can place of carbon nanotubes, can be actually used in the spendable any application of carbon nanotube, and obtain foreseeable excellent results usually.
Carbon nano-structured also have required length.Carbon nano-structured length is the length along the hole that the hole axle is measured.If carbon nano-structured keeping flat or horizontal positioned, then carbon nano-structured length are carbon nano-structured height.One preferred embodiment in, the carbon nano-structured qualification that carbon nano-structured length is formed by the template nano particle of substantially spherical.The carbon nano-structured length that usually only has near carbon nano-structured external diameter that forms by the spherical template nano particle.Basic polymerization uniformly and/or carbonization can obtain such result around the template nano particle.For the structure that appears as carbon nano ring in the TEM image, its length is no more than the external diameter of carbon nano ring usually, and this is to increase with essentially identical speed usually because of length in polymerization process and external diameter.Length less than or to approximate the carbon nano-structured of external diameter be favourable because compare with for example carbon nanotube, they have bigger surface-area, and/or they more help the diffusion of reactant and reaction product.
Another carbon nano-structured characteristics of the present invention are the walls that form non-tubular shape.Shown in the SEM image of the TEM image of Figure 1A, 1B and 1C and Fig. 4 A and 4B, graphite linings forms solid substantially wall.This and other people prepare the carbon nano-structured trial that the end of carbon nanotube wherein is connected to form ring and form contrast.The disadvantageous tension force of carbon nano-structured generation with tubular wall can influence the structural integrity of nanostructure and other character.For example, the report in the document proposes node (kinks) in the circular nano pipe and has prevented to form diameter carbon nano-structured less than 70 nanometers.In any situation, term " carbon nano ring " should be got rid of the ring texture that is connected to form by the end that carbon nanotube is relative with " carbon nano-structured ".
Except the good electron transitivity, carbon nano-structured also have high porosity and high surface area of the present invention.Absorption is conciliate adsorption isothermal line and is shown the carbon nano-structured mesopore material that formed.Carbon nano-structured BET specific surface area can be about 80-400 rice
2/ gram is preferably greater than about 120 meters
2/ gram is about 200 meters usually
2/ gram is apparently higher than common 100 meters of carbon nanotube
2/ gram.
Make the carbon nano-structured solid support material that can be used as nanoparticle catalyst according to the carbon nano-structured high surface area of the present invention preparation and high porosity.Reactant and/or the electronics enhancing by the diffusion of solid support material raising substrate and electron transport are to the efficient of nano particle catalytic surface.Therefore, the nano particle that loads on the conventional carriers (for example carbon black) of loaded catalyst ratio of the present invention has better performance.
Described in No. the 11/351620th, the U. S. application submitted on February 9th, 2006, according to the carbon nano-structured another kind of purposes of the present invention preparation be as join in the polymer materials the solid particulate filler (for example, substitute as carbon black or carbon nanotube), the content of this reference is incorporated into this.The polymer materials of filling like this with the preliminary test shows of the polymer materials of carbon nano-structured filling of the present invention and with the carbon black of a great deal of or carbon nano-tube filled polymer phase ratio, its surface resistivity obviously descends.
V. embodiment
Following examples provide and have prepared carbon nano-structured prescription of the present invention.
Embodiment 1 has described the carbon nano-structured method of solid catalysis preparation of nanoparticles of using.Use 2.24 gram iron powders, 7.70 gram citric acids and 400 ml waters to prepare the ferrous solution of 0.1M.This is contained in the bottle of remaining silent of iron mixture on being placed on shaking table mixed 7 days, briefly interrupted (for example 1-2 minute) is opened container midway, makes hydrogen overflow the vapor space in the air admission bottle.In the mixture of 6.10 gram Resorcinols and 9.0 gram formaldehyde, slowly add 100 milliliters of ferrous solutions.Under vigorous stirring, drip 30 milliliters of ammonium hydroxide.The pH value of gained suspension is 10.26.Then slurries were solidified 3.5 hours 80-90 ℃ (oil bath), it is carbon nano-structured to form intermediate.Carbon nano-structured by filter collecting intermediate, dried overnight in baking oven then, then under nitrogen gas stream 1150 ℃ of carbonizations 3 hours.The gained composite nanostructure is at 5M HNO
3Middle backflow 6-8 hour, use 300 ml mixture (H then
2O/H
2SO
4/ KMnO
4, mol ratio=1: 0.01: 0.003) handled 3 hours at 90 ℃.At last, wash with water carbon nano-structured, in baking oven dry 3 hours.Above-mentioned steps produces 1.1 gram carbon nano-structured products (being carbon nano ring and/or hollow many squashes shape structure).
Analyze prepare among the embodiment 1 carbon nano-structured then, at first use tem analysis, analyze with SEM then.The TEM pictorial display of the nano-rings of embodiment 1 is in Figure 1A-1C, 2A-2B and 3A-3B.From the TEM image as can be seen, as if method of the present invention can produce the nanostructure that is mainly annular carbon nano-structured (i.e. " nano-rings ") and single-size.The SEM image of Fig. 4 A-4B of same carbon nanostructure shows that nanostructure is actually spheric (or class spheric), rather than annular.Because shown in the TEM image, spherical multi-wall carbon nano-tube structure has hole in the centre, so they are not solid " nano-onions (nano onions) ".
Embodiment 2
In embodiment 2, prepare carbon nano-structuredly according to the method that is similar to embodiment 1, different is that intermediate is carbon nano-structured 850 ℃ of carbonizations 4 hours.This step produces 1.04 gram carbon nano-structured products (being spherical multi-wall carbon nano-tube structure and/or carbon nano ring).
The present invention can implement with other specific form under the situation that does not depart from its spirit or principal character.Described embodiment can be considered to just be used for explanation in every respect and not be construed as limiting.Therefore, scope of the present invention is shown by the description of appended claims rather than front.Implication and all changes within the equivalency range at claims are included within its scope.
Claims (25)
1. one kind prepares carbon nano-structured method, and it comprises:
(i) form a plurality of catalytic templating nano particles by following steps:
(a) make a plurality of precursor catalyst atoms and a plurality of organic dispersing agent molecular reaction, form the catalyst atoms of complexing;
(b) appoint the catalyst atoms of complexing or make the catalyst atoms of complexing form the template nano particle;
(ii) carbon nano-structured by in the presence of the template nano particle, making carbon precursor polymerization reaction take place form one or more intermediates;
(iii) make the carbon nano-structured carbonization of intermediate, form a plurality of composite nanostructures; With
(iv) from composite nanostructure, remove the template nano particle, obtain carbon nano-structured.
2. the method for claim 1 is characterized in that, described catalyst atoms comprises at least a in iron, nickel or the cobalt.
3. the method for claim 1, it is characterized in that, described dispersant molecule can combine with catalyst atoms, and comprises at least one and be selected from following functional group: hydroxyl, carboxyl, carbonyl, amine, acid amides, nitrile, the nitrogen with lone-pair electron, amino acid, mercaptan, sulfonic acid, sulfonic acid halide, carboxylic acid halides and their combination.
4. the method for claim 1, it is characterized in that, described dispersant molecule comprise be selected from following at least a: oxalic acid, oxysuccinic acid, propanedioic acid, toxilic acid, Succinic Acid, oxyacetic acid, lactic acid, glucose, citric acid, pectin, Mierocrystalline cellulose, thanomin, mercaptoethanol, the 2-mercaptoacetate, glycine, the sulfo group phenylcarbinol, sulfosalicylic acid, the sulfo group beneze methane thiol, the sulfo group benzene methanamine, polyacrylic ester, polyvinyl benzoate, poly-sulfuric acid vinyl ester, poly-sulfonic acid vinyl acetate, poly-carbonic acid bis-phenol ester, polybenzimidazole, polypyridine, the sulfonated polyethylene terephthalate, with their combination.
5. the method for claim 1 is characterized in that, but described carbon precursor comprises hydrothermal solution polymeric organic substrate.
6. method as claimed in claim 5 is characterized in that, but described hydrothermal solution polymeric organic substrate comprises at least a in citric acid, vinylformic acid, phenylformic acid, acrylate, divinyl, vinylbenzene or the styracin.
7. the method for claim 1 is characterized in that, described carbon precursor comprises at least a in Resorcinol-formaldehyde gel, phenol resins, melamine-formaldehyde gel, poly-(furfuryl alcohol) or poly-(vinyl cyanide).
8. the method for claim 1 is characterized in that, described template nano particle with form before the carbon precursor mixes.
9. the method for claim 1 is characterized in that, carries out under a certain temperature of described carbonization in about 500 ℃ to 2500 ℃ scopes.
10. the method for claim 1 is characterized in that, by carrying out etching with at least a in acid or the alkali, removes at least a portion template nano particle from composite nanostructure.
11. the composition of a material, it comprises carbon nano-structured according to the method for claim 1 preparation.
12. a method for preparing loaded catalyst, it comprises metal catalyst particles is arranged on according on the method for claim 1 preparation carbon nano-structured.
13. method as claimed in claim 12 is characterized in that, described metal catalyst particles comprises at least a precious metal.
14. the loaded catalyst of a foundation method preparation as claimed in claim 12.
15. one kind with the carbon nano-structured method of produced in high yields, it comprises:
(i) provide a plurality of solid catalysis template nano particles, it is mainly by the organic dispersing agent molecular composition of the metal catalyst atoms of one or more types and optional one or more types;
(ii) solid catalysis template nano particle is mixed with the carbon precursor, make the carbon precursor polymeric, it is carbon nano-structured to form a plurality of intermediates;
(iii) make the carbon nano-structured carbonization of intermediate, form a plurality of composite nanostructures; With
(iv) from composite nanostructure, remove the template nano particle, obtain carbon nano-structured.
16. method as claimed in claim 15 is characterized in that, described metal catalyst atoms comprises at least a in iron, nickel or the cobalt.
17. method as claimed in claim 15, it is characterized in that, described dispersant molecule can combine with catalyst atoms, and comprises at least one and be selected from following functional group: hydroxyl, carboxyl, carbonyl, amine, acid amides, nitrile, the nitrogen with lone-pair electron, amino acid, mercaptan, sulfonic acid, sulfonic acid halide, carboxylic acid halides and their combination.
18. method as claimed in claim 15, it is characterized in that, described dispersant molecule comprise be selected from following at least a: oxalic acid, oxysuccinic acid, propanedioic acid, toxilic acid, Succinic Acid, oxyacetic acid, lactic acid, glucose, citric acid, pectin, Mierocrystalline cellulose, thanomin, mercaptoethanol, the 2-mercaptoacetate, glycine, the sulfo group phenylcarbinol, sulfosalicylic acid, the sulfo group beneze methane thiol, the sulfo group benzene methanamine, polyacrylic ester, polyvinyl benzoate, poly-sulfuric acid vinyl ester, poly-sulfonic acid vinyl acetate, poly-carbonic acid bis-phenol ester, polybenzimidazole, polypyridine, sulfonated polyethylene terephthalate and their combination.
19. method as claimed in claim 15 is characterized in that, but described carbon precursor comprises hydrothermal solution polymeric organic substrate.
20. method as claimed in claim 19 is characterized in that, but described hydrothermal solution polymeric organic substrate comprises at least a in citric acid, vinylformic acid, phenylformic acid, acrylate, divinyl, vinylbenzene or the styracin.
21. method as claimed in claim 15 is characterized in that, described carbon precursor comprises at least a in Resorcinol-formaldehyde gel, phenol resins, melamine-formaldehyde gel, poly-(furfuryl alcohol) or poly-(vinyl cyanide).
22. method as claimed in claim 15 is characterized in that, carries out under a certain temperature of described carbonization in about 500 ℃ to 2500 ℃ scopes.
23. a method for preparing loaded catalyst, it comprises metal catalyst particles is arranged on according on method as claimed in claim 22 preparation carbon nano-structured.
24. method as claimed in claim 23 is characterized in that, described metal catalyst particles comprises at least a precious metal.
25. the composition of a material, it is a plurality of carbon nano-structured that it method that comprises that foundation may further comprise the steps prepares:
(i) provide a plurality of solid catalysis template nano particles, it is mainly by the organic dispersing agent molecular composition of the metal catalyst atoms of one or more types and optional one or more types;
(ii) solid catalysis template nano particle is mixed with the carbon precursor, make the carbon precursor polymeric, it is carbon nano-structured to form a plurality of intermediates;
(iii) make the carbon nano-structured carbonization of intermediate, form a plurality of composite nanostructures; With
(iv) from composite nanostructure, remove the template nano particle, obtain carbon nano-structured.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72432305P | 2005-10-06 | 2005-10-06 | |
| US60/724,323 | 2005-10-06 | ||
| US11/539,042 | 2006-10-05 |
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| CN101282905A true CN101282905A (en) | 2008-10-08 |
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| WO2013082770A1 (en) * | 2011-12-07 | 2013-06-13 | 北京化工大学 | Carbon nanoring and preparation method therefor |
| CN104016328A (en) * | 2013-02-28 | 2014-09-03 | 中国科学院大连化学物理研究所 | Method for preparing nitrogen-containing carbon nano tube |
| CN105347329A (en) * | 2015-12-09 | 2016-02-24 | 中国科学院青岛生物能源与过程研究所 | Preparation method of carbon nano-rings |
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| CN116119653A (en) * | 2023-02-08 | 2023-05-16 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Multifunctional anti-aggregation quenched carbon nano onion and preparation method and application thereof |
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| US8834982B2 (en) | 2011-12-07 | 2014-09-16 | Beijing University Of Chemical Technology | Carbon nanoring and method for preparing the same |
| CN104016328A (en) * | 2013-02-28 | 2014-09-03 | 中国科学院大连化学物理研究所 | Method for preparing nitrogen-containing carbon nano tube |
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| CN116119653A (en) * | 2023-02-08 | 2023-05-16 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Multifunctional anti-aggregation quenched carbon nano onion and preparation method and application thereof |
| CN116119653B (en) * | 2023-02-08 | 2023-11-21 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Multifunctional anti-aggregation quenched carbon nano onion and preparation method and application thereof |
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