CN103569994A - Processing method for single-wall carbon nanotube - Google Patents
Processing method for single-wall carbon nanotube Download PDFInfo
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Abstract
The invention provides a processing method for single-wall carbon nanotube. The processing method for single-wall carbon nanotube comprises the following steps: (1) in the presence of a solvent, orderly contacting single-wall carbon nanotubes with a surfactant and a dispersant to make the content of single dispersed single-wall carbon nanotube be larger than 50 wt%, the preferable content of dispersed single-wall carbon nanotube being 50 wt% to 60 wt%, wherein the single-wall carbon nanotube can disperse into the solvent, and the surfactant and the dispersant can dissolve in the solvent; (2) carrying out a density gradient centrifugation treatment for the dispersed-state single-wall carbon nanotubes obtained in the step (1). The processing method can effectively separate single-wall carbon nanotubes with different structural properties, and thus establish a foundation for subsequent systematic researches on structural properties of single-wall carbon nanotube.
Description
Technical field
The present invention relates to a kind for the treatment of process of Single Walled Carbon Nanotube.
Background technology
Carbon nanotube is unique one dimension tracheary element structure nano material that nanometer scale, axial dimension can reach micron dimension as a kind of radial dimension, is a kind of One-dimensional Quantum material with typical stratiform hollow structure feature being comprised of hexagonal carbon ring structure unit.Wherein, Single Walled Carbon Nanotube (SWNTs) consists of individual layer cylinder shape graphite linings, compares with multi-walled carbon nano-tubes (MWNTs), and the distribution range of its diameter is less, defect is less and have higher uniformity consistency.Due to the structure of SWNTs uniqueness, it not only has low density, good electrical properties, also has the multifrequency natures such as good thermostability and chemical stability.In field of biology, the one dimension Nano structure of SWNTs uniqueness becomes a kind of desirable nano-medicament carrier.Research shows, the matrix material of carbon nanotube can be newborn muscle skeleton and carrier are provided, and can induce the directed differentiation of bone cells, also can be used as the medium of multifunctional bio transmitter and near infrared ray selective killing cancer cells.
In recent years, the research of carbon nanotube biological effect shows that its preparation method and structural qualitative diversity have brought many difficulties to correlative study, and wherein, the many factors such as the purity of carbon nanotube, size and aggregation extent all may affect its cell behavior.Becker etc. have prepared with DNA parcel carbon nanotube the stable dispersion solution system that keeps carbon nano tube surface electronic structure, have investigated the size difference of cellular uptake carbon nanotube.Research shows, for carbon nanotube, picked-up has length selectivity to cell, and the carbon nanotube that is less than (180 ± 17) nm generally can all be absorbed by cell.And the research of Simon etc. shows that long MWNTs and short MWNTs have stronger cytotoxicity.Smart etc. think that the toxic side effect of carbon nanotube may come from the metal catalyst using while preparing, and kish catalyzer not only can be effectively removed in chemically modified, can also introduce bioactive molecules, therefore can improve the biocompatibility of carbon nanotube.The research of Sayes etc. shows that cytotoxicity can reduce along with the increase of SWNTs sidewall functionalization degree.Duortier etc. think that functionalization SWNTs has no significant effect the function of immunocyte.And causing current correlative study to occur that an important factor of significant difference is, its research object is different sources or functionalization mode, and the SWNTs mixture that comprises multiple different structure character.Due to the specific aim research lacking different structure character in same system (as caliber, state of aggregation, length etc.) SWNTs component, current result of study does not have comparability each other, cannot really from the angle of the textural property of SWNTs own, illustrate difference and the mechanism of its biological effect.As can be seen here, for carbon nanotube, from various different angles such as synthetic method, size of particles, surface properties and forms, systematically study its biological effect and toxic mechanism, just can contribute to understand in depth the impact of carbon nanotube on environment, health comprehensively.Therefore, for the preparation in enormous quantities of the SWNTs component of same source different structure character, become one of key factor of dealing with problems, and the structure of the separation system of pointed SWNTs seems most important.
From current correlative study, because carbon nanotube has multiple physico-chemical property and biological characteristics, for the systematic Study of the carbon nanotube of different structure character, will be a later research emphasis.As mentioned above, how realizing the preparation in enormous quantities of carbon nanotube of different structure character separated will be a key point of restriction correlative study.The forward position research of recent domestic also shows, the separation preparation of carbon nanotube has been subject to paying attention to more and more and paying close attention to.Wherein, carrying out separate study particularly important according to the difference of carbon nanotube structure character, is the main point of penetration of research at present.Common separation method comprises dielectrophoresis method, chromatography and selective growth method etc., but these several separation methods all have certain limitation.For example, dielectrophoresis method is separated mainly for semi-conductor and conductive carbon nanotube, and Application Areas is narrower; Chromatography complex pretreatment is higher to sample requirement; And in selective growth method, the problems such as functionalization, sample pretreatment and recovery, plant and instrument and output are affected its separating effect, thereby limited follow-up application.Yet, it is worth noting, density gradient centrifugation is separated into an important method for carbon nanotube separation in recent years.Although the method is started late in carbon nanotube separation Application Areas, simply controlled due to its operating process, becomes the focus in carbon nanotube separation field gradually.Arnold etc. utilize the use of density gradient centrifugation and blending surface dispersion agent first, have realized the separation for the carbon nanotube of different electrical properties or caliber.Yet the existence due to a large amount of state of aggregation tube banks in carbon nanotube, makes its effective band fuzzy, ratio is low, thereby makes its final separating effect and output be subject to very big restriction.Dai etc. utilize density gradient centrifugation to carry out length separation for ultrashort SWNTs.But due to the singularity in sample size, there is certain gap in its textural property and one dimension carbon nanotube, thereby is unsuitable for applying.Weisman etc. utilize density gradient centrifugation to realize the chiral separation of SWNTs first.Yet due to the existence of a large amount of state of aggregation tube banks, greatly limited its isolated yield equally, made separated product cannot really move towards at present application.Therefore,, in research at present, how to improve the monodispersity of carbon nanotube, the ratio of reduction state of aggregation carbon nano-tube bundle becomes a key that improves gradient centrifugation isolated yield.
Summary of the invention
The object of the invention is in order to overcome the above-mentioned defect of prior art, and provide a kind of can be by the treatment process of the Single Walled Carbon Nanotube of the Single Walled Carbon Nanotube separation of different structure character.
The treatment process that the invention provides a kind of Single Walled Carbon Nanotube, the method comprises the following steps:
(1) under solvent exists, Single Walled Carbon Nanotube is contacted with dispersion agent with tensio-active agent successively, the content that makes to obtain single dispersion Single Walled Carbon Nanotube is not less than 50 % by weight, is preferably the dispersed Single Walled Carbon Nanotube of 50 % by weight-60 % by weight, and described Single Walled Carbon Nanotube can be dispersed in solvent and described tensio-active agent and dispersion agent can be dissolved in this solvent;
(2) dispersed Single Walled Carbon Nanotube step (1) being obtained is carried out density gradient centrifugation separation.
The present inventor finds, under solvent exists, Single Walled Carbon Nanotube is contacted with dispersion agent with tensio-active agent successively, can make Single Walled Carbon Nanotube be dispersed in well in tensio-active agent and dispersion agent, obtain the higher system of single dispersion Single Walled Carbon Nanotube content, infer its reason, may be due to: Single Walled Carbon Nanotube is contacted with tensio-active agent, can access the Single Walled Carbon Nanotube tube bank of stable dispersion in tensio-active agent, after contacting with dispersion agent again, interaction between described dispersion agent and Single Walled Carbon Nanotube tube bank can enter in Single Walled Carbon Nanotube tube bank described dispersion agent at an easy rate, tube bank is effectively split, reduce the ratio of state of aggregation Single Walled Carbon Nanotube, thereby obtain the Single Walled Carbon Nanotube system of high dispersive.Further, the Single Walled Carbon Nanotube that the success of the Single Walled Carbon Nanotube system of this polymolecularity is prepared as further acquisition different structure character provides possibility.
A preferred embodiment of the invention, when dispersed Single Walled Carbon Nanotube being carried out to the method for density gradient centrifugation separation, comprise: first dispersed Single Walled Carbon Nanotube is carried out to the separation of first step density gradient centrifugation, make described Single Walled Carbon Nanotube carry out layering according to the difference of pipe diameter size and state of aggregation; Respectively the different Single Walled Carbon Nanotube layer of gained is carried out again to second stage density gradient centrifugation separated, when the Single Walled Carbon Nanotube that makes to obtain through the separation of first step density gradient centrifugation is carried out layering according to the difference of length, the Single Walled Carbon Nanotube with different structure character can be carried out to effective separation.According to another kind of preferred implementation of the present invention, when the twice separated density gradient reagent adopting of density gradient centrifugation is the solution containing Visipaque 320, and when the concentration of described density gradient reagent is followed successively by 8-12 % by weight, 15-35 % by weight and 55-65 % by weight from top to bottom, the Single Walled Carbon Nanotube with different structure character can be carried out more effectively separated.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the separated schematic diagram of first step density gradient centrifugation, and wherein, (A) schematic diagram of first step density gradient centrifugation separation, (B) is the design sketch of first step density gradient centrifugation separation;
Fig. 2 is the result of the Near-Infrared Photoluminescence spectrum of four kinds of components obtaining of embodiment 1 separation;
Fig. 3 is the atomic force microscope of four kinds of components and the result of length distribution that embodiment 1 separation obtains;
Fig. 4 is the atomic force microscope of each component and the result of length distribution that the component A in embodiment 1 obtains after second stage density gradient centrifugation is separated with C.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The treatment process of Single Walled Carbon Nanotube provided by the invention comprises the following steps:
(1) under solvent exists, Single Walled Carbon Nanotube is contacted with dispersion agent with tensio-active agent successively, the content that makes to obtain single dispersion Single Walled Carbon Nanotube is not less than 50 % by weight, is preferably the dispersed Single Walled Carbon Nanotube of 50 % by weight-60 % by weight, and described Single Walled Carbon Nanotube can be dispersed in solvent and described tensio-active agent and dispersion agent can be dissolved in this solvent;
(2) dispersed Single Walled Carbon Nanotube step (1) being obtained is carried out density gradient centrifugation separation.
Wherein, described Single Walled Carbon Nanotube can exist with powder type, now, described under solvent exists, the form that Single Walled Carbon Nanotube is contacted with dispersion agent with tensio-active agent successively comprises Single Walled Carbon Nanotube is contacted with dispersant solution with surfactant soln successively;
Described Single Walled Carbon Nanotube also can exist with dispersion, and in described dispersion liquid, the content of single dispersion Single Walled Carbon Nanotube, not higher than 10 % by weight, is preferably 6-8 % by weight; Now, described under solvent exists, the form that Single Walled Carbon Nanotube is contacted with dispersion agent with tensio-active agent successively comprises single-walled carbon nanotube dispersion liquid is contacted with dispersion agent or dispersant solution with tensio-active agent or surfactant soln successively.
According to the present invention, in Single Walled Carbon Nanotube after contacting with dispersion agent with tensio-active agent successively, in the content of single dispersion Single Walled Carbon Nanotube and pending Single Walled Carbon Nanotube, the content of single dispersion Single Walled Carbon Nanotube can record by scanning electronic microscope, also can obtain by the weight of Single Walled Carbon Nanotube of single dispersion and the ratio calculation of the gross weight of Single Walled Carbon Nanotube obtaining after density gradient centrifugation separation.
According to the present invention, pending Single Walled Carbon Nanotube can be commercially available, and for example, can be the Single Walled Carbon Nanotube purchased from epoch nanometer company of section in Chengdu; Also can prepare by existing method, concrete preparation method is known to the skilled person, and at this, will repeat no more.As mentioned above, described Single Walled Carbon Nanotube can exist with the form of powder, also can exist with the form of dispersion liquid; When the form with dispersion liquid exists, the Single Walled Carbon Nanotube in dispersion liquid and the part by weight of dispersion medium are as being 1:1-3, and described dispersion medium can be selected from one or more in water, ethanol, methyl alcohol and acetone.
According to the present invention, the kind of described tensio-active agent and consumption can be that the routine of this area selects, and for example, the described Single Walled Carbon Nanotube of 1g of take is benchmark, and the consumption of described tensio-active agent can be 10-15g.Described tensio-active agent can be selected from one or more in Sodium cholic acid, cholic acid potassium, Sodium desoxycholate, Septochol potassium, sodium lauryl sulphate, dodecyl sulphate potassium, Sodium palmityl sulfate, hexadecyl hydrosulfate potassium, sodium laurylsulfonate, dodecyl sodium sulfonate potassium, sodium cetanesulfonate and hexadecyl potassium sulfonate.Described tensio-active agent can directly be used, and also can use with the form of solution; When the form with solution is used, the concentration of described tensio-active agent can be 5-10mg/mL.
The present invention is not particularly limited the condition that described Single Walled Carbon Nanotube is contacted with tensio-active agent, as long as can make described Single Walled Carbon Nanotube stable dispersion in described tensio-active agent, as a rule, the condition of described contact comprises Contact Temperature and duration of contact.Usually, the raising of Contact Temperature is conducive to the dispersion of carbon nanotube powder, but the too high structure that may destroy Single Walled Carbon Nanotube of temperature, therefore, the temperature of described contact is preferably 20-25 ℃; The prolongation of duration of contact can improve the dispersiveness of described carbon nanotube powder in tensio-active agent, but duration of contact, the long amplitude that degree of scatter is improved was also not obvious, therefore, considered effect and efficiency, was preferably 8-12 hour described duration of contact.
According to the present invention, the kind of described dispersion agent and consumption also can be that the routine of this area selects, and for example, the described Single Walled Carbon Nanotube of 1g of take is benchmark, and the consumption of described dispersion agent can be 1-2g.Described dispersion agent can be selected from one or more in rhodamine, fluorescein isothiocyanate and 1-pyrene butyric acid.Described dispersion agent can be used separately, also can use with the form of solution; When the form with solution is used, the concentration of described dispersion agent can be 200-400 μ g/mL.In addition, when described tensio-active agent and dispersion agent are all used with the form of its solution, introducing for fear of impurity in Single Walled Carbon Nanotube sepn process, preferably, the solvent species that dissolves described tensio-active agent and dispersion agent is identical, and can be selected from one or more in water, ethanol, methyl alcohol and acetone.When the form of pending carbon nanotube with dispersion liquid exists, and when tensio-active agent and dispersion agent are used with the form of solution, preferably, dispersion medium in carbon nano tube dispersion liquid is identical with the solvent species that dissolves described tensio-active agent and dispersion agent, and can be selected from one or more in water, ethanol, methyl alcohol and acetone.
The condition that the present invention contacts with dispersion agent the product obtaining after Single Walled Carbon Nanotube is contacted with tensio-active agent is not particularly limited, as long as can access the dispersed Single Walled Carbon Nanotube that the content of single dispersion Single Walled Carbon Nanotube is not less than 50%, is preferably 50-60%, for example, it can be 2-6 ℃ that the condition of described contact generally includes Contact Temperature, and can be 12-24 hour described duration of contact.
According to the present invention, in step (2), dispersed Single Walled Carbon Nanotube is carried out to the kind of the Single Walled Carbon Nanotube that the method for density gradient centrifugation separation can obtain as required and carry out choose reasonable, preferably, the method of dispersed Single Walled Carbon Nanotube being carried out to density gradient centrifugation separation comprises: first dispersed Single Walled Carbon Nanotube is carried out to the separation of first step density gradient centrifugation, make described Single Walled Carbon Nanotube carry out layering according to the difference of pipe diameter size and state of aggregation; Respectively the different Single Walled Carbon Nanotube layer of gained is carried out again to second stage density gradient centrifugation separated, make the Single Walled Carbon Nanotube obtaining through the separation of first step density gradient centrifugation carry out layering according to the difference of length.
Particularly, dispersed Single Walled Carbon Nanotube is carried out after the separation of described first step density gradient centrifugation, along the direction of centrifuge tube, can obtain successively from top to bottom single dispersion Single Walled Carbon Nanotube, the single dispersion Single Walled Carbon Nanotube of Large Diameter Pipeline, the state of aggregation Single Walled Carbon Nanotube of pipe with small pipe diameter.Described state of aggregation Single Walled Carbon Nanotube refers to the tube bank that is flocked together and formed by 5-15 root Single Walled Carbon Nanotube.In addition, because the density of the different state of aggregation Single Walled Carbon Nanotube of structural integrity is different, therefore, through first step density gradient centrifugation after separating, the state of aggregation carbon nanotube that is distributed in the lowest layer can also carry out separation, obtains Single Walled Carbon Nanotube and the incomplete Single Walled Carbon Nanotube of structure of structural integrity.; exactly; through first step density gradient centrifugation after separating, along the direction of centrifuge tube, can obtain successively from top to bottom single dispersion Single Walled Carbon Nanotube, the single dispersion Single Walled Carbon Nanotube of Large Diameter Pipeline, the state of aggregation Single Walled Carbon Nanotube of structural integrity, the incomplete state of aggregation Single Walled Carbon Nanotube of structure of pipe with small pipe diameter.Respectively the different Single Walled Carbon Nanotube layer of gained is carried out again to second stage density gradient centrifugation separated, respectively the single dispersion Single Walled Carbon Nanotube of pipe with small pipe diameter, the single dispersion Single Walled Carbon Nanotube of Large Diameter Pipeline, state of aggregation Single Walled Carbon Nanotube are carried out to second stage density gradient centrifugation separated, can access the Single Walled Carbon Nanotube that length is different.It should be noted that, as mentioned above, through first step density gradient centrifugation after separating, described state of aggregation Single Walled Carbon Nanotube can also be separated into state of aggregation Single Walled Carbon Nanotube and the incomplete state of aggregation Single Walled Carbon Nanotube of structure of structural integrity.When state of aggregation Single Walled Carbon Nanotube being carried out to second stage density gradient centrifugation separation, can respectively the state of aggregation Single Walled Carbon Nanotube of structural integrity and the incomplete state of aggregation Single Walled Carbon Nanotube of structure be carried out to second stage density gradient separation, also the mixture of the state of aggregation Single Walled Carbon Nanotube of structural integrity and the incomplete Single Walled Carbon Nanotube of structure can be carried out to second stage density gradient separation.
In addition, those skilled in the art should hold intelligible, if the single caliber of pending Single Walled Carbon Nanotube is all consistent with length, after density gradient centrifugation separation, described Single Walled Carbon Nanotube only obtains single dispersion Single Walled Carbon Nanotube, state of aggregation Single Walled Carbon Nanotube according to the difference separation of state of aggregation so, to these those skilled in the art, all can know, at this, will repeat no more.
The present invention is not particularly limited the condition of described first step density gradient centrifugation separation, as long as dispersed Single Walled Carbon Nanotube can be carried out to layering according to the difference of pipe diameter size and state of aggregation, for example, the condition of described first step density gradient centrifugation separation comprises that centrifugal rotational speed can be 30000-40000rpm, centrifugation time can be 8-10 hour, density gradient reagent can be the solution containing Visipaque 320, and the concentration of described density gradient reagent is followed successively by 8-12 % by weight, 15-35 % by weight and 55-65 % by weight from top to bottom.Those skilled in the art should hold intelligible, and density gradient centrifugation separation is the separated centrifuging according to density of carrying out in density gradient reagent, and each component can be according to its density distribution in the liquid layer identical with himself density.The density gradient reagent that concentration is respectively to 55-65 % by weight, 15-35 % by weight and 8-12 % by weight adds in centrifuge tube successively, after adding again dispersed Single Walled Carbon Nanotube, each component in described dispersed Single Walled Carbon Nanotube is distributed in different layers because density is different, thereby the different Single Walled Carbon Nanotube of textural property is carried out to separation.
The present invention is also not particularly limited the condition of described second stage density gradient centrifugation separation, as long as can respectively the Single Walled Carbon Nanotube layer obtaining be carried out to layering according to the difference of length after the separation of first step density gradient centrifugation, for example, the condition of described second stage density gradient centrifugation separation comprises that centrifugal rotational speed can be 30000-40000rpm, centrifugation time can be 4-6 hour, density gradient reagent can be the solution containing Visipaque 320, and the concentration of described density gradient reagent is followed successively by 8-12 % by weight, 15-35 % by weight and 55-65 % by weight from top to bottom.
According to the present invention, for by the Impurity removal in Single Walled Carbon Nanotube, and improve the water-soluble of described Single Walled Carbon Nanotube, under preferable case, the method contacts described Single Walled Carbon Nanotube and carries out pre-treatment before being also included in described Single Walled Carbon Nanotube being contacted with tensio-active agent with acidic solution.The kind of described acidic solution and consumption can be selected for the routine of this area; For example, can be selected from one or more in hydrochloric acid, aqueous nitric acid and aqueous sulfuric acid, the concentration of described acidic solution can be selected in the larger context and change, and for example, can be 5-7mol/L; Take 1g Single Walled Carbon Nanotube as benchmark, and the consumption of described acidic solution can be 1000-2000mL.More preferably, the condition that described Single Walled Carbon Nanotube is contacted with acidic solution comprises that temperature can be 120-150 ℃, and the time can be 6-12 hour.Further, the product water obtaining after preferably Single Walled Carbon Nanotube can also being contacted with acidic solution washs, and to remove residual acidic solution, and filters, is dried.
Below will describe the present invention by embodiment.
In following examples and comparative example, photoluminescence spectroscopy is purchased from HORIBA company, and model is HORIBA Jobin Yvon NanoLog
tM; Atomic force microscope is purchased from Digital Instruments company, and model is Dimension 3100; Raman spectrometer is purchased from Renishaw plc company, and model is Renishaw Micro-Raman Spectroscopy System; The content of single dispersion Single Walled Carbon Nanotube is measured by scanning electronic microscope (purchased from Hitachi company, model is S-4700).
This embodiment is for illustrating the treatment process of Single Walled Carbon Nanotube provided by the invention and processing the Single Walled Carbon Nanotube obtaining.
(1) pre-treatment of Single Walled Carbon Nanotube:
By 0.1g Single Walled Carbon Nanotube (purchased from Chengdu Zhong Ke nanometer Time Inc., the powder type of take exists) being 7mol/L with 150mL concentration, aqueous nitric acid mixes, and back flow reaction was filtered after 12 hours at 120 ℃, filter residue is washed with water 3 times, and filter, be dried, obtain pretreated Single Walled Carbon Nanotube powder;
(2) dispersion of Single Walled Carbon Nanotube:
At 25 ℃, the lauryl sodium sulfate aqueous solution that the product that step (1) is obtained and 200mL concentration are 5mg/mL was uniformly mixed after 8 hours, solution temperature is down to 4 ℃, and to add 500mL concentration be that the Rhodamine 123 aqueous solution of 200 μ g/mL continues to be uniformly mixed 12 hours, the dispersed Single Walled Carbon Nanotube that to obtain weight ratio that single dispersion Single Walled Carbon Nanotube accounts for total Single Walled Carbon Nanotube be 50%;
(3) gradient centrifugation is separated:
The Visipaque 320 aqueous solution that by 12mL concentration is respectively 60 % by weight, 30 % by weight and 10 % by weight adds in centrifuge tube successively, the dispersed Single Walled Carbon Nanotube again 1mL step (2) being obtained adds in this centrifuge tube and carries out the separation of first step density gradient centrifugation, the condition of described first step density gradient centrifugation separation comprises that centrifugal rotational speed is 35000rpm, centrifugation time is 9 hours, and acquired results as shown in Figure 1.As can be seen from the figure, after the separation of first step gradient centrifugation, four bands clearly be can obtain, component A, B component, component C and component D are denoted as successively from top to bottom.Adopt photoluminescence spectroscopy, atomic force microscope and Raman spectrum to carry out structural characterization to above-mentioned four kinds of components, wherein, as shown in Figure 2, the result of atomic force microscope as shown in Figure 3 for the test result of Near-Infrared Photoluminescence spectrograph.From the result of Fig. 2, can find out, component A and B can observe near-infrared fluorescent signal, and wherein, the chirality of component A forms and comprises (6,5), (7,5), (7,6), (8,3), (8,4), (8,6), (8,7), (9,4), (9,5), (10,2), (10,5), (11,3) and (12,1), the chirality of B component forms and comprises (7,6) and (10,2); Component C and D do not observe significant near-infrared fluorescent signal, and the fluorescent quenching mechanism that this causes with state of aggregation conforms to, and as can be seen here, component A and B are single dispersion Single Walled Carbon Nanotube, and component C and D are state of aggregation Single Walled Carbon Nanotube.From the result of Fig. 3, can find out, the average caliber of component A is 0.8nm, and the average caliber of B component is 1.5nm, and the average tube bank size of component C is 4nm, and the average tube bank size of component D is 6nm.From the structure of Raman spectrum, can find out, component C-structure is complete, and component D structure is imperfect, and wherein, component C is the tube bank being polymerized by 5-10 root Single Walled Carbon Nanotube, and component D is the tube bank being polymerized by 10-15 root Single Walled Carbon Nanotube.As can be seen here, after the separation of first step gradient centrifugation, obtain successively from top to bottom the single dispersion Single Walled Carbon Nanotube A of pipe with small pipe diameter, the state of aggregation Single Walled Carbon Nanotube C of the single dispersion Single Walled Carbon Nanotube B of Large Diameter Pipeline, structural integrity and the incomplete state of aggregation Single Walled Carbon Nanotube of structure D;
Get four centrifuge tubes, in every centrifuge tube, all adding successively 12mL concentration is 60 % by weight, the Visipaque 320 aqueous solution of 30 % by weight and 10 % by weight, the single dispersion Single Walled Carbon Nanotube A of the pipe with small pipe diameter respectively 1mL being obtained again, the single dispersion Single Walled Carbon Nanotube B of Large Diameter Pipeline, the state of aggregation Single Walled Carbon Nanotube C of structural integrity adds in these four centrifuge tubes with the incomplete state of aggregation Single Walled Carbon Nanotube of structure D and to carry out second stage density gradient centrifugation separated, wherein, the condition of described second stage density gradient centrifugation separation comprises that centrifugal rotational speed is 36000rpm, centrifugation time is 5 hours, component A obtains three kinds of different component A1, A2, A3, wherein, the result of atomic force microscope shows that the length range of component A1 is 200-400nm, the length range of component A2 is 400-800nm, the length of component A3 is about 1 μ m, B component obtains three kinds of different B component 1, B2, B3, and wherein, the result of atomic force microscope shows that the length range of B component 1 is 200-500nm, and the length range of B component 2 is 500-1000nm, and the length range of B component 3 is 1 μ m, component C obtains three kinds of different component C1, C2, C3, and wherein, the result of atomic force microscope shows that the length range of component C1 is 50-100nm, and the length range of component C2 is 200-800nm, and the length of component C3 is about 1 μ m, component D obtains three kinds of different component D1, D2, D3, and wherein, the result of atomic force microscope shows that the length range of component D1 is 50-100nm, and the length range of component D2 is 100-500nm, and the length range of component D3 is 500nm-1 μ m.
This embodiment is for illustrating the treatment process of Single Walled Carbon Nanotube provided by the invention and processing the Single Walled Carbon Nanotube obtaining.
(1) pre-treatment of Single Walled Carbon Nanotube:
By 0.1g Single Walled Carbon Nanotube (purchased from Chengdu Zhong Ke nanometer Time Inc., the powder type of take exists) being 5mol/L with 150mL concentration, aqueous sulfuric acid mixes, and back flow reaction was filtered after 6 hours at 150 ℃, filter residue is washed with water 3 times, and filter, be dried, obtain pretreated Single Walled Carbon Nanotube;
(2) dispersion of Single Walled Carbon Nanotube:
At 20 ℃, the Sodium cholic acid aqueous solution that the product that step (1) is obtained and 300mL concentration are 5mg/mL was uniformly mixed after 12 hours, solution temperature is down to 4 ℃, and to add 250mL concentration be that the fluorescein isothiocyanate aqueous solution of 400 μ g/mL continues to be uniformly mixed 24 hours, the dispersed Single Walled Carbon Nanotube that to obtain weight ratio that single dispersion Single Walled Carbon Nanotube accounts for total Single Walled Carbon Nanotube be 60%;
(3) gradient centrifugation is separated:
The Visipaque 320 aqueous solution that by 12mL concentration is respectively 55 % by weight, 15 % by weight and 8 % by weight adds in centrifuge tube successively, the dispersed Single Walled Carbon Nanotube again 1mL step (2) being obtained adds in this centrifuge tube and carries out the separation of first step density gradient centrifugation, the condition of described first step density gradient centrifugation separation comprises that centrifugal rotational speed is 30000rpm, and centrifugation time is 10 hours.After the separation of first step gradient centrifugation, four bands clearly be can obtain, component A, B component, component C and component D are denoted as successively from top to bottom.Adopt photoluminescence spectroscopy, atomic force microscope and Raman spectrum to carry out structural characterization to above-mentioned four kinds of components.From the test result of photoluminescence spectroscopy, can find out, component A and B can observe near-infrared fluorescent signal, component C and D do not observe significant near-infrared fluorescent signal, the fluorescent quenching mechanism that this causes with state of aggregation conforms to, as can be seen here, component A and B are single dispersion Single Walled Carbon Nanotube, and component C and D are state of aggregation Single Walled Carbon Nanotube.From the result of atomic force microscope, can find out, the average caliber of component A is 0.8nm, and the average caliber of B component is 1.5nm, and the average tube bank size of component C is 4nm, and the average tube bank size of component D is 6nm.From the structure of Raman spectrum, can find out, component C-structure is complete, and component D structure is imperfect, and wherein, component C is the tube bank being polymerized by 5-10 root Single Walled Carbon Nanotube, and component D is the tube bank being polymerized by 10-15 root Single Walled Carbon Nanotube.As can be seen here, after the separation of first step gradient centrifugation, obtain successively from top to bottom the single dispersion Single Walled Carbon Nanotube A of pipe with small pipe diameter, the state of aggregation Single Walled Carbon Nanotube C of the single dispersion Single Walled Carbon Nanotube B of Large Diameter Pipeline, structural integrity and the incomplete state of aggregation Single Walled Carbon Nanotube of structure D;
Get four centrifuge tubes, in every centrifuge tube, all adding successively 12mL concentration is 55 % by weight, the Visipaque 320 aqueous solution of 15 % by weight and 8 % by weight, the single dispersion Single Walled Carbon Nanotube A of the pipe with small pipe diameter respectively 1mL being obtained again, the single dispersion Single Walled Carbon Nanotube B of Large Diameter Pipeline, the state of aggregation Single Walled Carbon Nanotube C of structural integrity adds in these four centrifuge tubes with the incomplete state of aggregation Single Walled Carbon Nanotube of structure D and to carry out second stage density gradient centrifugation separated, wherein, the condition of described second stage density gradient centrifugation separation comprises that centrifugal rotational speed is 30000rpm, centrifugation time is 6 hours, component A obtains three kinds of different component A1, A2, A3, wherein, the result of atomic force microscope shows that the length range of component A1 is 200-400nm, the length range of component A2 is 400-800nm, the length range of component A3 is 1 μ m, B component obtains three kinds of different B component 1, B2, B3, and wherein, the result of atomic force microscope shows that the length range of B component 1 is 200-500nm, and the length range of B component 2 is 500-1000nm, and the length range of B component 3 is 1 μ m, component C obtains three kinds of different component C1, C2, C3, and wherein, the result of atomic force microscope shows that the length range of component C1 is 50-100nm, and the length range of component C2 is 200-800nm, and the length range of component C3 is 1 μ m, component D obtains three kinds of different component D1, D2, D3, and wherein, the result of atomic force microscope shows that the length range of component D1 is 50-100nm, and the length range of component D2 is 100-500nm, and the length range of component D3 is 500nm-1 μ m.
Embodiment 3
This embodiment is for illustrating the treatment process of Single Walled Carbon Nanotube provided by the invention and processing the Single Walled Carbon Nanotube obtaining.
(1) pre-treatment of Single Walled Carbon Nanotube:
By 0.1g Single Walled Carbon Nanotube (purchased from Chengdu Zhong Ke nanometer Time Inc., form with dispersion liquid exists, wherein, the dispersion medium of this dispersion liquid is that the weight ratio of water and Single Walled Carbon Nanotube and water is 1:2, in this dispersion liquid, the content of single dispersion Single Walled Carbon Nanotube is 7 % by weight) being 6mol/L with 150mL concentration, aqueous nitric acid mixes, and back flow reaction was filtered after 9 hours at 135 ℃, filter residue is washed with water 3 times, and filter, be dried, obtain pretreated Single Walled Carbon Nanotube powder;
(2) dispersion of Single Walled Carbon Nanotube:
At 22 ℃, the Septochol sodium water solution that the product that step (1) is obtained and 150mL concentration are 8mg/mL was uniformly mixed after 10 hours, solution temperature is down to 4 ℃, and to add 350mL concentration be that the 1-pyrene butyric acid aqueous solution of 300 μ g/mL continues to be uniformly mixed 20 hours, the dispersed Single Walled Carbon Nanotube that to obtain weight ratio that single dispersion Single Walled Carbon Nanotube accounts for total Single Walled Carbon Nanotube be 55%;
(3) gradient centrifugation is separated:
The Visipaque 320 aqueous solution that by 12mL concentration is respectively 65 % by weight, 35 % by weight and 12 % by weight adds in centrifuge tube successively, the dispersed Single Walled Carbon Nanotube again 1mL step (2) being obtained adds in this centrifuge tube and carries out the separation of first step density gradient centrifugation, the condition of described first step density gradient centrifugation separation comprises that centrifugal rotational speed is 40000rpm, and centrifugation time is 8 hours.After the separation of first step gradient centrifugation, four bands clearly be can obtain, component A, B component, component C and component D are denoted as successively from top to bottom.Adopt photoluminescence spectroscopy, atomic force microscope and Raman spectrum to carry out structural characterization to above-mentioned four kinds of components.From the test result of photoluminescence spectroscopy, can find out, component A and B can observe near-infrared fluorescent signal, component C and D do not observe significant near-infrared fluorescent signal, the fluorescent quenching mechanism that this causes with state of aggregation conforms to, as can be seen here, component A and B are single dispersion Single Walled Carbon Nanotube, and component C and D are state of aggregation Single Walled Carbon Nanotube.From the result of atomic force microscope, can find out, the average caliber of component A is 0.8nm, and the average caliber of B component is 1.5nm, and the average tube bank size of component C is 3nm, and the average tube bank size of component D is 7nm.From the structure of Raman spectrum, can find out, component C-structure is complete, and component D structure is imperfect, and wherein, component C is the tube bank being polymerized by 5-10 root Single Walled Carbon Nanotube, and component D is the tube bank being polymerized by 10-15 root Single Walled Carbon Nanotube.As can be seen here, after the separation of first step gradient centrifugation, obtain successively from top to bottom the single dispersion Single Walled Carbon Nanotube A of pipe with small pipe diameter, the state of aggregation Single Walled Carbon Nanotube C of the single dispersion Single Walled Carbon Nanotube B of Large Diameter Pipeline, structural integrity and the incomplete state of aggregation Single Walled Carbon Nanotube of structure D;
Get four centrifuge tubes, in every centrifuge tube, all adding successively 12mL concentration is 65 % by weight, the Visipaque 320 aqueous solution of 35 % by weight and 12 % by weight, the single dispersion Single Walled Carbon Nanotube A of the pipe with small pipe diameter respectively 1mL being obtained again, the single dispersion Single Walled Carbon Nanotube B of Large Diameter Pipeline, the state of aggregation Single Walled Carbon Nanotube C of structural integrity adds in these four centrifuge tubes with the incomplete state of aggregation Single Walled Carbon Nanotube of structure D and to carry out second stage density gradient centrifugation separated, wherein, the condition of described second stage density gradient centrifugation separation comprises that centrifugal rotational speed is 40000rpm, centrifugation time is 6 hours, component A obtains three kinds of different component A1, A2, A3, wherein, the result of atomic force microscope shows that the length range of component A1 is 200-400nm, the length range of component A2 is 400-800nm, the length of component A3 is about 1 μ m, B component obtains three kinds of different B component 1, B2, B3, and wherein, the result of atomic force microscope shows that the length range of B component 1 is 200-500nm, and the length range of B component 2 is 500-1000nm, and the length range of B component 3 is 1 μ m, component C obtains three kinds of different component C1, C2, C3, and wherein, the result of atomic force microscope shows that the length range of component C1 is 50-100nm, and the length range of component C2 is 200-800nm, and the length of component C3 is about 1 μ m, component D obtains three kinds of different component D1, D2, D3, and wherein, the result of atomic force microscope shows that the length range of component D1 is 50-100nm, and the length range of component D2 is 100-500nm, and the length range of component D3 is 500nm-1 μ m.
Embodiment 4
This embodiment is for illustrating the treatment process of Single Walled Carbon Nanotube provided by the invention and processing the Single Walled Carbon Nanotube obtaining.
According to the method for embodiment 1, Single Walled Carbon Nanotube is carried out to separation, different, do not comprise Single Walled Carbon Nanotube is carried out to pretreated step.After the separation of first step density gradient centrifugation, obtain successively from top to bottom the single dispersion Single Walled Carbon Nanotube A of pipe with small pipe diameter, the state of aggregation Single Walled Carbon Nanotube C of the single dispersion Single Walled Carbon Nanotube B of Large Diameter Pipeline, structural integrity and the incomplete state of aggregation Single Walled Carbon Nanotube of structure D.After the density gradient centrifugation separation of the second stage, component A obtains three kinds of different component A1, A2, A3, and wherein, the result of atomic force microscope shows that the length range of component A1 is 200-400nm, the length range of component A2 is 400-800nm, and the length range of component A3 is 1 μ m; B component obtains three kinds of different B component 1, B2, B3, and wherein, the result of atomic force microscope shows that the length range of B component 1 is 200-500nm, and the length range of B component 2 is 500-1000nm, and the length range of B component 3 is 1 μ m; Component C obtains three kinds of different component C1, C2, C3, and wherein, the result of atomic force microscope shows that the length range of component C1 is 50-100nm, and the length range of component C2 is 200-800nm, and the length range of component C3 is 1 μ m; Component D obtains three kinds of different component D1, D2, D3, and wherein, the result of atomic force microscope shows that the length range of component D1 is 50-100nm, and the length range of component D2 is 100-500nm, and the length range of component D3 is 500nm-1 μ m.
Comparative example 1
This comparative example is used for the reference treatment process of instruction book wall carbon nano tube and processes the Single Walled Carbon Nanotube obtaining.
According to the method for embodiment 1, Single Walled Carbon Nanotube is carried out to separation, different, in the dispersion steps of Single Walled Carbon Nanotube, the lauryl sodium sulfate aqueous solution of Rhodamine 123 same concentrations, same volume for the aqueous solution is substituted.Result demonstration, Single Walled Carbon Nanotube solution system dispersiveness is not significantly improved, and wherein, the content of state of aggregation Single Walled Carbon Nanotube is about 90%.
Comparative example 2
This comparative example is used for the reference treatment process of instruction book wall carbon nano tube and processes the Single Walled Carbon Nanotube obtaining.
According to the method for embodiment 1, Single Walled Carbon Nanotube is carried out to separation, different, in the dispersion steps of Single Walled Carbon Nanotube, the Rhodamine 123 aqueous solution of same concentrations, same volume for lauryl sodium sulfate aqueous solution is substituted.Result shows, Single Walled Carbon Nanotube solution system water-soluble very low, and a large amount of Single Walled Carbon Nanotube are separated out with precipitation forms.
As can be seen from the above results, adopt the method for the present invention can be by the effective separation of carrying out having in the Single Walled Carbon Nanotube of different structure character, thereby lay a good foundation for the systematic study of the follow-up Single Walled Carbon Nanotube for different structure character.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a treatment process for Single Walled Carbon Nanotube, the method comprises the following steps:
(1) under solvent exists, Single Walled Carbon Nanotube is contacted with dispersion agent with tensio-active agent successively, the content that makes to obtain single dispersion Single Walled Carbon Nanotube is not less than 50 % by weight, is preferably the dispersed Single Walled Carbon Nanotube of 50 % by weight-60 % by weight, and described Single Walled Carbon Nanotube can be dispersed in solvent and described tensio-active agent and dispersion agent can be dissolved in this solvent;
(2) dispersed Single Walled Carbon Nanotube step (1) being obtained is carried out density gradient centrifugation separation.
2. method according to claim 1, wherein, described Single Walled Carbon Nanotube exists with powder type, described under solvent exists, the form that Single Walled Carbon Nanotube is contacted with dispersion agent with tensio-active agent successively comprises Single Walled Carbon Nanotube is contacted with dispersant solution with surfactant soln successively.
3. method according to claim 1, wherein, described Single Walled Carbon Nanotube exists with dispersion, and in described dispersion liquid, the content of single dispersion Single Walled Carbon Nanotube, not higher than 10 % by weight, is preferably 6-8 % by weight; Described under solvent exists, the form that Single Walled Carbon Nanotube is contacted with dispersion agent with tensio-active agent successively comprises single-walled carbon nanotube dispersion liquid is contacted with dispersion agent or dispersant solution with tensio-active agent or surfactant soln successively.
4. according to the method described in any one in claim 1-3, wherein, the described Single Walled Carbon Nanotube of 1g of take is benchmark, and the consumption of described tensio-active agent is 10-15g; Preferably, described tensio-active agent is selected from one or more in Sodium cholic acid, cholic acid potassium, Sodium desoxycholate, Septochol potassium, sodium lauryl sulphate, dodecyl sulphate potassium, Sodium palmityl sulfate, hexadecyl hydrosulfate potassium, sodium laurylsulfonate, dodecyl sodium sulfonate potassium, sodium cetanesulfonate and hexadecyl potassium sulfonate.
5. according to the method described in any one in claim 1-3, wherein, the condition that described Single Walled Carbon Nanotube is contacted with tensio-active agent comprises that Contact Temperature is 20-25 ℃, and be 8-12 hour duration of contact.
6. according to the method described in any one in claim 1-3, wherein, the described Single Walled Carbon Nanotube of 1g of take is benchmark, and the consumption of described dispersion agent is 1-2g; Preferably, described dispersion agent is selected from one or more in rhodamine, fluorescein isothiocyanate and 1-pyrene butyric acid.
7. according to the method described in claim 1,2,3 or 4, wherein, the condition that the product obtaining after Single Walled Carbon Nanotube is contacted with tensio-active agent contacts with dispersion agent comprises that Contact Temperature is 2-6 ℃, and be 12-24 hour duration of contact.
8. method according to claim 1, wherein, in step (2), the method of dispersed Single Walled Carbon Nanotube being carried out to density gradient centrifugation separation comprises: first dispersed Single Walled Carbon Nanotube is carried out to the separation of first step density gradient centrifugation, make described Single Walled Carbon Nanotube carry out layering according to the difference of pipe diameter size and state of aggregation; Respectively the different Single Walled Carbon Nanotube layer of gained is carried out again to second stage density gradient centrifugation separated, make the Single Walled Carbon Nanotube obtaining through the separation of first step density gradient centrifugation carry out layering according to the difference of length.
9. method according to claim 8, wherein, the condition of described first step density gradient centrifugation separation comprises: centrifugal rotational speed is 30000-40000rpm, centrifugation time is 8-10 hour, density gradient reagent is the solution containing Visipaque 320, and the concentration of described density gradient reagent is followed successively by 8-12 % by weight, 15-35 % by weight and 55-65 % by weight from top to bottom.
10. method according to claim 8 or claim 9, wherein, the condition of described second stage density gradient centrifugation separation comprises: centrifugal rotational speed is 30000-40000rpm, centrifugation time is 4-6 hour, density gradient reagent is the solution containing Visipaque 320, and the concentration of described density gradient reagent is followed successively by 8-12 % by weight, 15-35 % by weight and 55-65 % by weight from top to bottom.
11. methods according to claim 8, wherein, the method contacts described Single Walled Carbon Nanotube and carries out pre-treatment before being also included in described Single Walled Carbon Nanotube being contacted with tensio-active agent with acidic solution; Preferably, the condition that described Single Walled Carbon Nanotube is contacted with acidic solution comprises that Contact Temperature is 120-150 ℃, and be 6-12 hour duration of contact.
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