CN102179182A - Method for preparing carbon nanofiber membrane - Google Patents
Method for preparing carbon nanofiber membrane Download PDFInfo
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- CN102179182A CN102179182A CN2011100776042A CN201110077604A CN102179182A CN 102179182 A CN102179182 A CN 102179182A CN 2011100776042 A CN2011100776042 A CN 2011100776042A CN 201110077604 A CN201110077604 A CN 201110077604A CN 102179182 A CN102179182 A CN 102179182A
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Abstract
The invention provides a method for preparing a carbon nanofiber membrane, which comprises the following steps of: a) mixing tellurium nanowires and glucose in aqueous solution, and performing carbonation reaction to obtain a carbon-coated tellurium nano cable; b) adding hydrochloric acid and hydrogen peroxide into the carbon-coated tellurium nano cable, and performing oxidation reaction to obtain carbon nanofibers; and c) dispersing the carbon nanofibers in a solvent o obtain slurry, coating the slurry on a support material, and drying to obtain the carbon nanofiber membrane. The prepared carbon nanofibers are uniform in diameter, so tht the obtained carbon nanofiber membrane has narrow pore diameter distribution; by controlling synthetic conditions of the nanofibers, carbon nanofibers with different diameters can be obtained, so that the pore diameter of the carbon nanofiber membrane is controllable, and the carbon nanofiber membrane is better applied to a membrane separation technology. In addition, the surface of the carbon nanofiber membrane is rich in hydrophilic groups, the water circulation quantity of the membrane is large, and the efficiency is high during membrane separation.
Description
Technical field
The invention belongs to technical field of nano material, relate in particular to a kind of preparation method of carbon nano-fiber film.
Background technology
Membrane separation technique is a Selective Separation of utilizing film separation, the purifying of realizing the different component of feed liquid and the technology that process such as concentrates, have that efficient, energy-saving and environmental protection, molecular level are filtered, filter process is simple, be easy to advantage such as control, be widely used in food, medicine, biology, environmental protection, chemical industry, metallurgy, the energy, oil, water treatment, electronics, field such as bionical.
The usefulness that film separates depends on the attribute of film itself, wherein, by monodimension nanometer material, owing to having bigger specific area, has filtration and separating effect preferably as the film of formation such as nano wire, nanotube, nanofiber.Prior art discloses and multiplely has been used to filter and the 1-dimention nano film that separates, as Holland " membrane science " (Journal of Membrane Science, 581 pages of 2006 281 phases) reported a kind of polyvinylidene fluoride nanometer fiber membrane with the method for electrostatic spinning preparation, this film can be used for filtering the particulate of removing in the aqueous solution, but, the diameter of the polyvinylidene fluoride nanometer fiber that method of electrostatic spinning makes is thicker, and skewness, the membrane pore size that obtains is bigger, can only be used to filter the particle of micron-scale.Germany " advanced material " (Advanced Materials, 785 pages of 2007 19 phases) a kind of high efficiency filter film of being made up of ceramic nanofibers is disclosed, be the titanium dioxide nano thread of tens nanometers at first at Woelm Alumina substrate upper berth one deck diameter, repaving one deck diameter then is the AlOOH superfine nano fiber of several nanometers, the combined filtration film that assembling obtains having three-decker, this film has very high water flux, but the diameter of this film is uncontrollable, the film of critical dimension be can only obtain, its filtration and separating effect reduced.Britain's " nature material " (Nature Materials, 610 pages of 2004 3 phases) by improving the used chemical vapor depsotition equipment of carbon nano-tube, prepared a kind of tubular film of forming by vertical CNT, the diameter of this tubular film and length can reach Centimeter Level, has effect preferably when being used for removing by filter the microbial contamination material such as bacterium, virus of water body, but the aperture of this film is unadjustable, and preparation cost is higher.
The carbon nano-fiber of diameter between 10nm～500nm is a kind of new nano material, it is except possessing the characteristic of general carbon fiber, outside performances such as low-density, high specific strength, high ratio modulus, high conduction and heat conduction, also have advantages such as defects count is few, specific area big, compact structure.Carbon nano-fiber has a good application prospect in fields such as catalyst, electrode material, sorbing material, parting material, composite, hydrogen storage material, absorbing materials.But present and no-trump carbon nano-fiber is assembled into the report of carbon nano-fiber film, also the carbon nano-fiber film is not used for the report of membrane separation technique.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of carbon nano-fiber film, and the aperture of the carbon nano-fiber film of the present invention's preparation is adjustable, and pore-size distribution is narrower, is used for having bigger circulation when film separates, and separating effect is better.
The invention provides a kind of preparation method of carbon nano-fiber film, may further comprise the steps:
A) tellurium nano-wire is mixed in the aqueous solution with glucose, carry out obtaining carbon coating tellurium nano-cable after the carburizing reagent;
B) coat adding hydrochloric acid and hydrogen peroxide in the tellurium nano-cable to described carbon, carry out obtaining carbon nano-fiber after the oxidation reaction;
C) described carbon nano-fiber is scattered in obtains slurry in the solvent, described slurry is applied on the backing material, obtain the carbon nano-fiber film after the drying.
Preferably, in the described step a), the mass ratio of described tellurium nano-wire and described glucose is (0.10～0.20): (60～70).
Preferably, in the described step a), the temperature of described carburizing reagent is 160 ℃～220 ℃.
Preferably, in the described step a), the time of described carburizing reagent is 15h～80h.
Preferably, in the described step b), the ratio that described carbon coats the amount of substance of the amount of substance of the quality of tellurium nano-cable, described hydrochloric acid and described hydrogen peroxide is (3g～8g): (0.2mol～0.8mol): (0.2mol～0.8mol).
Preferably, in the described step c), described solvent is water or ethanol.
Preferably, in the described step c), the ratio of the quality of described carbon nano-fiber and the volume of described solvent is (5g～10g): 1L.
Preferably, in the described step c), described backing material is a polytetrafluoroethylene (PTFE).
Preferably, in the described step a), described tellurium nano-wire prepares in accordance with the following methods:
Polyvinylpyrrolidone, sodium tellurite, hydrazine hydrate and ammoniacal liquor are mixed in the aqueous solution, obtain tellurium nano-wire after the reaction.
Preferably, the temperature of described reaction is 160 ℃～200 ℃, and the time of described reaction is 3h～5h.
Compared with prior art, the present invention at first mixes with glucose tellurium nano-wire in the aqueous solution, carries out obtaining carbon coating tellurium nano-wire after the carburizing reagent; Coat adding hydrochloric acid and hydrogen peroxide in the tellurium nano-cable to described carbon then, will obtain the comparatively carbon nano-fiber of homogeneous of diameter after the tellurium oxidation wherein; Described carbon nano-fiber is scattered in obtains slurry in the solvent, described slurry is applied on the backing material, obtain the carbon nano-fiber film of self-supporting after the drying.The carbon nano-fiber diameter of the present invention's preparation is homogeneous comparatively, makes the pore-size distribution of the carbon nano-fiber film that obtains narrower; Synthesis condition by the control carbon nano-fiber can obtain the different carbon nano-fiber of diameter, thereby make that the aperture of carbon nano-fiber film is controlled, more helps it and is applied in the membrane separation technique.In addition, hydrophilic radical is rich on described carbon nano-fiber film surface, and the water flux density of film is very big, and efficient is higher when being used for the film separation.
Experiment shows, the present invention's preparation, be that the carbon nano-fiber film that the carbon nano-fiber of 50nm forms has good pliability, mechanical stability and hydrophily by diameter, the flow velocity when filter sizes is the gold grain of 25nm under 80kPa pressure is 900L/ (hm
2), can be used for the separation of different size nano particle.
Description of drawings
The stereoscan photograph of the carbon nano-fiber that Fig. 1 provides for the embodiment of the invention 1;
The stereoscan photograph of the carbon nano-fiber film that Fig. 2 provides for the embodiment of the invention 1;
The UV, visible light optical absorption spectra figure of the carbon nano-fiber membrane filtration 5nm gold grain that Fig. 3 provides for the embodiment of the invention 1;
The UV, visible light optical absorption spectra figure of the carbon nano-fiber membrane filtration 25nm gold grain that Fig. 4 provides for the embodiment of the invention 1;
The stereoscan photograph of the carbon nano-fiber that Fig. 5 provides for the embodiment of the invention 2;
The stereoscan photograph of the carbon nano-fiber that Fig. 6 provides for the embodiment of the invention 3;
The stereoscan photograph of the carbon nano-fiber that Fig. 7 provides for the embodiment of the invention 4;
The stereoscan photograph of the carbon nano-fiber that Fig. 8 provides for the embodiment of the invention 5;
The stereoscan photograph of the carbon nano-fiber that Fig. 9 provides for the embodiment of the invention 6.
The specific embodiment
The invention provides a kind of preparation method of carbon nano-fiber film, may further comprise the steps:
A) tellurium nano-wire is mixed in the aqueous solution with glucose, carry out obtaining carbon coating tellurium nano-cable after the carburizing reagent;
B) coat adding hydrochloric acid and hydrogen peroxide in the tellurium nano-cable to described carbon, carry out obtaining carbon nano-fiber after the oxidation reaction;
C) described carbon nano-fiber is scattered in obtains slurry in the solvent, described slurry is applied on the backing material, obtain the carbon nano-fiber film after the drying.
The present invention is a template with the tellurium nano-wire, is that raw material has obtained carbon coating tellurium nano-cable with glucose; Be oxidant then with the hydrogen peroxide, the tellurium core that under the condition that hydrochloric acid exists carbon is coated in the tellurium nano-cable is removed, and obtains carbon nano-fiber; With carbon nano-fiber system film, obtain the carbon nano-fiber film of self-supporting again.
The present invention at first mixes with glucose tellurium nano-wire in the aqueous solution, carry out obtaining carbon coating tellurium nano-cable after the carburizing reagent.In this process, glucose carries out carburizing reagent and generates carbon, and carbon forms carbon parcel tellurium nano-cable with tellurium nano-wire parcel back.Comparing with fructose with polysaccharide such as starch, maltose, sucrose, is that raw material carries out the formation that carburizing reagent can be avoided the carbon ball with glucose, makes the carbon coating tellurium nano-cable size that obtains comparatively even, thereby obtains the comparatively carbon nano-fiber of homogeneous of diameter.
According to the present invention, the mass ratio of described tellurium nano-wire and described glucose is preferably (0.10～0.20): (60～70), more preferably (0.12～0.18): (63～68); The mass concentration of described tellurium nano-wire in the aqueous solution is preferably 0.10g/L～0.20g/L, more preferably 0.12g/L～0.18g/L; The mass concentration of described glucose in the described aqueous solution is preferably 60g/L～70g/L, more preferably 63g/L～68g/L.The temperature of described carburizing reagent is preferably 160 ℃～220 ℃, more preferably 160 ℃～200 ℃, most preferably is 160 ℃～180 ℃; The time of described carburizing reagent is preferably 15h～80h, more preferably 18h～72h.The time of carburizing reagent and temperature are the key factors that influences the carbon nano-fiber membrane aperture, and those skilled in the art can carry out the adjustment of carbonization time and temperature according to the use needs, thereby obtain the adjustable carbon nano-fiber film in aperture.
In the present invention, preferably preparation in accordance with the following methods of described tellurium nano-wire:
Polyvinylpyrrolidone, sodium tellurite, hydrazine hydrate and ammoniacal liquor are mixed in the aqueous solution, obtain tellurium nano-wire after the reaction.
Polyvinylpyrrolidone and sodium tellurite is soluble in water, back adding hydrazine hydrate and ammoniacal liquor stir, react after stirring, in course of reaction, sodium tellurite by hydrazine hydrate reduction, obtains having the nano wire of the semiconductor tellurium of high-specific surface area under the effect of high molecular surfactant polyvinylpyrrolidone and ammoniacal liquor.The mass ratio of described polyvinylpyrrolidone and described sodium tellurite is preferably (8～48): (2.2～6.6), more preferably (10～40): (2.5～6); The mass concentration of described polyvinylpyrrolidone in the aqueous solution is preferably 8g/L～48g/L, more preferably 10g/L～40g/L; The mass concentration of described sodium tellurite in the aqueous solution is preferably 2.2g/L～6.6g/L, more preferably 2.5g/L～6g/L.The quality optimization of described hydrazine hydrate be polyvinylpyrrolidone, sodium tellurite, water, hydrazine hydrate and ammoniacal liquor gross mass 2%～4%, more preferably 2.5%～3.5%; The quality optimization of described ammoniacal liquor be polyvinylpyrrolidone, sodium tellurite, water, hydrazine hydrate and ammoniacal liquor gross mass 1%～4%, more preferably 2%～3%.
After obtaining carbon parcel tellurium nano-cable, to wherein adding hydrochloric acid and hydrogen peroxide, hydrogen peroxide with the oxidation of described tellurium core after, obtain carbon nano-fiber.The easy and hydrogen peroxide generation oxidation reaction of tellurium core in the carbon parcel tellurium nano-cable, thus carbon nano-fiber obtained.The effect of hydrochloric acid is to make oxidation reaction more thorough, makes more homogeneous of the carbon nano-fiber diameter that obtains.Compare with saline oxidizing agents such as potassium bromate, potassium permanganate, potassium chlorate and sodium borohydrides, hydrogen peroxide does not contain inorganic ion, and is less to the influence of carbon nano-fiber.In the present invention, the ratio of the amount of substance of the quality of described tellurium parcel nano-cable, the amount of substance of described hydrochloric acid and described hydrogen peroxide is preferably (3g～8g): (0.2mol～0.8mol): (0.2mol～0.8mol), more preferably (4g～7g): (0.5mol～0.7mol): (0.5mol～0.7mol).
Carbon coats after the tellurium nano-cable finishes with the hydrogen peroxide reaction, with the reaction mixture centrifugation that obtains, solid product is washed, obtains carbon nano-fiber after the drying with distilled water.With the tellurium nano-wire is template, is raw material with glucose, is comparatively homogeneous of the carbon nano-fiber diameter for preparing of oxidant with the hydrogen peroxide that length is longer.
Described carbon nano-fiber is scattered in the solvent, obtains slurry, described slurry is applied on the backing material, can obtain the comparatively carbon nano-fiber film of homogeneous of self-supporting and aperture after the drying.According to the present invention, described solvent is preferably water or ethanol, more preferably water.The ratio of the quality of described carbon nano-fiber and the volume of described solvent is preferably (5g～10g): 1L, more preferably (6g～8g): 1L.
The effect of described backing material is to slurry provides support, and is convenient to form film behind the slurry drying.In the present invention, described backing material is preferably polytetrafluoroethylene (PTFE), more preferably the polytetrafluoroethylene (PTFE) circular trough.Described slurry evenly is applied on the described backing material, can obtains the carbon nano-fiber film of self-supporting after the drying.The present invention does not have particular restriction to described drying means, is preferably air dry 8h～36h at room temperature.
The carbon nano-fiber film that obtains is the self-supporting film, can peel off and exists with form of film from backing material, and it has pliability and mechanical stability, can use under the situation that pressure exists.
Because the carbon nano-fiber diameter of the present invention's preparation is homogeneous comparatively, the pore-size distribution of the carbon nano-fiber film that obtains is narrower; Synthesis condition by the control carbon nano-fiber can obtain the different carbon nano-fiber of diameter, thereby make that the aperture of carbon nano-fiber film is controlled, more helps it and is applied in the membrane separation technique.In addition, hydrophilic radical is rich on described carbon nano-fiber film surface, and the water flux density of film is very big, and efficient is higher when being used for the film separation.Experiment shows, the present invention's preparation, be that the carbon nano-fiber film that the carbon nano-fiber of 50nm forms has good pliability, mechanical stability and hydrophily by diameter, the flow velocity of filtration 25 nanogold particles is 900L/ (hm under 80kPa pressure
2), can be used for the separation of different size nano particle.
Because the aperture of carbon nano-fiber film provided by the invention is adjustable and pore-size distribution is narrower, carbon nano-fiber film provided by the invention can be used for the purifying of water, remove by filter solid particle and microorganisms such as bacterium, virus in the water, also can be used for based on the purifying of the nano particle of size with separate, can also be used for based on the purifying of the large biological molecule of size with separate.In addition, obtain the carbon nano-fiber film because the present invention is raw material with glucose through carburizing reagent, carboxyl is rich on the film surface, and the loading functional nano particle is made composite nano-fiber membrane as gold, silver, platinum etc., is used for Continuous Flow catalysis, sterilization etc.
In order to further specify the present invention, the preparation method of carbon nano-fiber film provided by the invention is described in detail below in conjunction with embodiment.
Below among each embodiment each raw material be from the market and buy.
With 1g polyvinylpyrrolidone and 92mg Na
2TeO
3Join in the 32mL water, after stirring, add 1.67mL hydrazine hydrate and 3.33mL ammoniacal liquor again, be stirred to phase-splitting and evenly be placed in the airtight container, be warming up to 180 ℃ of reaction 3h, obtain the Te nano wire, regulate the concentration of Te nano wire, obtain the Te nano wire aqueous solution of 0.18g/L;
The described Te nano wire of the 100mL aqueous solution is mixed with the D/W of 100mL67g/L, stir and be placed in the closed container, carry out the hydrothermal carbonization reaction under 160 ℃, behind the reaction 18h, be cooled to room temperature, obtain the Te nano-cable that C coats, regulate the concentration of the Te nano-cable of described C coating, obtain the Te nano-cable aqueous solution of 5g/L;
In the 100mLTe nano-cable aqueous solution, add the hydrochloric acid of 100mL0.5mol/L and the hydrogen peroxide of 100mL0.5mol/L, behind the stirring reaction, will obtain carbon nano-fiber after reactant mixture centrifugation, washing, the drying.
Described carbon nano-fiber is carried out field emission scanning electron microscope to be observed, the result is referring to Fig. 1, the stereoscan photograph of the carbon nano-fiber that Fig. 1 provides for the embodiment of the invention 1, as shown in Figure 1, it is comparatively even that the present invention obtains the diameter of carbon nano-fiber, for about 50nm, its length is longer, can reach tens microns.
Described carbon nano-fiber vigorous stirring is scattered in the water, obtains the slurry of 8g/L; The described slurry of 6mL evenly is applied in the polytetrafluoroethylene (PTFE) circular trough that internal diameter is 5cm, and at room temperature air dry 24h peels off described carbon nano-fiber from described ptfe surface, obtains the carbon nano-fiber film.
Described carbon nano-fiber film can be from polytetrafluoroethylene (PTFE) circular trough sur-face peeling, but and stable existence, it has good pliability and mechanical stability, has certain self-supporting function.
Described carbon nano-fiber film is carried out field emission scanning electron microscope to be observed, the result is referring to Fig. 2, the stereoscan photograph of the carbon nano-fiber film that Fig. 2 provides for the embodiment of the invention 1, as shown in Figure 2, it is comparatively even that the present invention obtains carbon nano-fiber film surface, and no aperture, slight crack or other defect exist.
Described carbon nano-fiber film is carried out the contact angle test, and its contact angle is 37 °, and contact angle is lower, and hydrophily is higher, can be used as filter membrane and uses.
With described carbon nano-fiber membrane filtration film, be that stoste is carried out filtration experiment to contain the aqueous solution that is of a size of the 25nm gold grain, the result shows that under 80kPa pressure, the flow velocity that filters the 25nm gold grain is 900L/ (hm
2).
With described carbon nano-fiber film is filter membrane, be that stoste is carried out filtration experiment to contain the aqueous solution that is of a size of 5nm and is of a size of the 25nm gold grain respectively, the result is referring to Fig. 3 and Fig. 4, the UV, visible light optical absorption spectra figure of the carbon nano-fiber membrane filtration 5nm gold grain that Fig. 3 provides for the embodiment of the invention 1, wherein, curve 31 is the UV, visible light optical absorption spectra figure of the stoste that contains the 5nm gold grain, and curve 32 is the UV, visible light optical absorption spectra figure that see through liquid of the stoste that contains the 5nm gold grain after filtering; The UV, visible light optical absorption spectra figure of the carbon nano-fiber membrane filtration 25nm gold grain that Fig. 4 provides for the embodiment of the invention 1, wherein, curve 41 is the UV, visible light optical absorption spectra figure of the stoste that contains the 25nm gold grain, and curve 42 is the UV, visible light optical absorption spectra figure that see through liquid of the stoste that contains the 25nm gold grain after filtering.As shown in Figure 3,95% 5nm gold grain all can see through described carbon nano-fiber film, and as shown in Figure 4, all the 25nm gold grain all can't see through described carbon nano-fiber film, and therefore, described carbon nano-fiber film can be used for separating nano-particles.
As filter membrane, is that stoste carry out nano particle separating experiment to contain the gold grain solution that is of a size of 5nm and is of a size of 25nm with described carbon nano-fiber film, and wherein, the mass ratio of 5nm gold grain and 25nm gold grain is 93.6: 6.4; The result shows that the mass percent of the 25nm gold grain in the concentrate increases to 34.5% by 6.4%.Concentrate is scattered in proceeds in the 20mL water to filter, the mass percent of 25nm gold grain increases to 91.4% in the concentrate that obtains.By above-mentioned experiment as can be known, carbon nano-fiber film provided by the invention can be realized the separation of nano particle.
With 1g polyvinylpyrrolidone and 92mg Na
2TeO
3Join in the 32mL water, after stirring, add 1.67mL hydrazine hydrate and 3.33mL ammoniacal liquor again, be stirred to phase-splitting and evenly be placed in the airtight container, be warming up to 180 ℃ of reaction 3h, obtain the Te nano wire, regulate the concentration of Te nano wire, obtain the Te nano wire aqueous solution of 0.18g/L;
The described Te nano wire of the 100mL aqueous solution is mixed with the D/W of 100mL67g/L, stir and be placed in the closed container, carry out the hydrothermal carbonization reaction under 160 ℃, behind the reaction 24h, be cooled to room temperature, obtain the Te nano-cable that C coats, regulate the Te nano-cable that described C coats, obtain the Te nano-cable aqueous solution of 5g/L;
In the 100mLTe nano-cable aqueous solution, add the hydrochloric acid of 100mL0.5mol/L and the hydrogen peroxide of 100mL0.5mol/L, behind the stirring reaction, will obtain carbon nano-fiber after reactant mixture centrifugation, washing, the drying.
Described carbon nano-fiber is carried out field emission scanning electron microscope to be observed, the result is referring to Fig. 5, the stereoscan photograph of the carbon nano-fiber that Fig. 5 provides for the embodiment of the invention 2, as shown in Figure 5, it is comparatively even that the present invention obtains the diameter of carbon nano-fiber, for about 71nm, its length is longer, can reach tens microns.
Described carbon nano-fiber vigorous stirring is scattered in the water, obtains the slurry of 8g/L; The described slurry of 6mL evenly is applied in the polytetrafluoroethylene (PTFE) circular trough that internal diameter is 5cm, and at room temperature air dry 24h peels off described carbon nano-fiber from described ptfe surface, obtains the carbon nano-fiber film.
Described carbon nano-fiber film can be peeled off from ptfe surface, but and stable existence, it has good pliability and mechanical stability, has certain self-supporting function.
Described carbon nano-fiber film is carried out field emission scanning electron microscope observe, the result shows that it is comparatively even that the present invention obtains carbon nano-fiber film surface, and no aperture, slight crack or other defect exist.
Described carbon nano-fiber film is carried out the contact angle test, and its contact angle is 37 °, and contact angle is lower, and hydrophily is higher, can be used as filter membrane and uses.
With described carbon nano-fiber membrane filtration film, be that stoste is carried out filtration experiment to contain the aqueous solution that is of a size of the 25nm gold grain, the result shows that under 80kPa pressure, the flow velocity that filters the 25nm gold grain is 5500L/ (hm
2).
With described carbon nano-fiber film is filter membrane, be that stoste is carried out filtration experiment to contain the aqueous solution that is of a size of 25nm and is of a size of the 60nm gold grain respectively, the result shows, 95% 25nm gold grain all can see through described carbon nano-fiber film, all the 60nm gold grain all can't see through described carbon nano-fiber film, therefore, described carbon nano-fiber film can be used for separating nano-particles.
As filter membrane, is that stoste carry out nano particle separating experiment to contain the gold grain solution that is of a size of 25nm and is of a size of 60nm with described carbon nano-fiber film, and wherein, the mass ratio of 25nm gold grain and 60nm gold grain is 77.4: 22.6; The result shows that the mass percent of the 60nm gold grain in the concentrate increases to 90.2% by 22.6%.By above-mentioned experiment as can be known, carbon nano-fiber film provided by the invention can be realized the separation of nano particle.
Embodiment 3
With 1g polyvinylpyrrolidone and 92mg Na
2TeO
3Join in the 32mL water, after stirring, add 1.67mL hydrazine hydrate and 3.33mL ammoniacal liquor again, be stirred to phase-splitting and evenly be placed in the airtight container, be warming up to 180 ℃ of reaction 3h, obtain the Te nano wire, regulate the concentration of Te nano wire, obtain the Te nano wire aqueous solution of 0.18g/L;
The described Te nano wire of the 100mL aqueous solution is mixed with the D/W of 100mL67g/L, stir and be placed in the closed container, carry out the hydrothermal carbonization reaction under 160 ℃, behind the reaction 36h, be cooled to room temperature, obtain the Te nano-cable that C coats, regulate the Te nano-cable that described C coats, obtain the Te nano-cable aqueous solution of 5g/L;
In the 100mLTe nano-cable aqueous solution, add the hydrochloric acid of 100mL0.5mol/L and the hydrogen peroxide of 100mL0.5mol/L, behind the stirring reaction, will obtain carbon nano-fiber after reactant mixture centrifugation, washing, the drying.
Described carbon nano-fiber is carried out field emission scanning electron microscope to be observed, the result is referring to Fig. 6, the stereoscan photograph of the carbon nano-fiber that Fig. 6 provides for the embodiment of the invention 3, as shown in Figure 6, it is comparatively even that the present invention obtains the diameter of carbon nano-fiber, for about 98nm, its length is longer, can reach tens microns.
Described carbon nano-fiber vigorous stirring is scattered in the water, obtains the slurry of 8g/L; The described slurry of 6mL evenly is applied in the polytetrafluoroethylene (PTFE) circular trough that internal diameter is 5cm, and at room temperature air dry 24h peels off described carbon nano-fiber from described ptfe surface, obtains the carbon nano-fiber film.
Described carbon nano-fiber film can be peeled off from ptfe surface, but and stable existence, it has good pliability and mechanical stability, has certain self-supporting function.
Described carbon nano-fiber film is carried out field emission scanning electron microscope observe, the result shows that it is comparatively even that the present invention obtains carbon nano-fiber film surface, and no aperture, slight crack or other defect exist.
Described carbon nano-fiber film is carried out the contact angle test, and its contact angle is 15 °, and contact angle is lower, and hydrophily is higher, can be used as filter membrane and uses.
With described carbon nano-fiber membrane filtration film, be that stoste is carried out filtration experiment to contain the aqueous solution that is of a size of the 150nm silica dioxide granule, the result shows that under 80kPa pressure, the flow velocity that filters the 150nm silica dioxide granule is 9800L/ (hm
2).
With described carbon nano-fiber film is filter membrane, be that stoste is carried out filtration experiment to contain the aqueous solution that is of a size of the 60nm gold grain and is of a size of the 150nm silica dioxide granule respectively, the result shows, 95% 60nm gold grain all can see through described carbon nano-fiber film, all the 150nm silica dioxide granule all can't see through described carbon nano-fiber film, therefore, described carbon nano-fiber film can be used for separating nano-particles.
Embodiment 4
With 1g polyvinylpyrrolidone and 92mg Na
2TeO
3Join in the 32mL water, after stirring, add 1.67mL hydrazine hydrate and 3.33mL ammoniacal liquor again, be stirred to phase-splitting and evenly be placed in the airtight container, be warming up to 180 ℃ of reaction 3h, obtain the Te nano wire, regulate the concentration of Te nano wire, obtain the Te nano wire aqueous solution of 0.18g/L;
The described Te nano wire of the 100mL aqueous solution is mixed with the D/W of 100mL67g/L, stir and be placed in the closed container, carry out the hydrothermal carbonization reaction under 160 ℃, behind the reaction 48h, be cooled to room temperature, obtain the Te nano-cable that C coats, regulate the Te nano-cable that described C coats, obtain the Te nano-cable aqueous solution of 5g/L;
In the 100mLTe nano-cable aqueous solution, add the hydrochloric acid of 100mL0.5mol/L and the hydrogen peroxide of 100mL0.5mol/L, behind the stirring reaction, will obtain carbon nano-fiber after reactant mixture centrifugation, washing, the drying.
Described carbon nano-fiber is carried out field emission scanning electron microscope to be observed, the result is referring to Fig. 7, the stereoscan photograph of the carbon nano-fiber that Fig. 7 provides for the embodiment of the invention 4, as shown in Figure 7, it is comparatively even that the present invention obtains the diameter of carbon nano-fiber, for about 132nm, its length is longer, can reach tens microns.
Described carbon nano-fiber vigorous stirring is scattered in the water, obtains the slurry of 8g/L; The described slurry of 6mL evenly is applied in the polytetrafluoroethylene (PTFE) circular trough that internal diameter is 5cm, and at room temperature air dry 24h peels off described carbon nano-fiber from described ptfe surface, obtains the carbon nano-fiber film.
Described carbon nano-fiber film can be peeled off from ptfe surface, but and stable existence, it has good pliability and mechanical stability, has certain self-supporting function.
Described carbon nano-fiber film is carried out field emission scanning electron microscope observe, the result shows that it is comparatively even that the present invention obtains carbon nano-fiber film surface, and no aperture, slight crack or other defect exist.
Described carbon nano-fiber film is carried out the contact angle test, and its contact angle is 0 °, and contact angle is lower, has Superhydrophilic, can be used as filter membrane and uses.
Embodiment 5
With 1g polyvinylpyrrolidone and 92mg Na
2TeO
3Join in the 32mL water, after stirring, add 1.67mL hydrazine hydrate and 3.33mL ammoniacal liquor again, be stirred to phase-splitting and evenly be placed in the airtight container, be warming up to 180 ℃ of reaction 3h, obtain the Te nano wire, regulate the concentration of Te nano wire, obtain the Te nano wire aqueous solution of 0.18g/L;
The described Te nano wire of the 100mL aqueous solution is mixed with the D/W of 100mL67g/L, stir and be placed in the closed container, carry out the hydrothermal carbonization reaction under 160 ℃, behind the reaction 60h, be cooled to room temperature, obtain the Te nano-cable that C coats, regulate the Te nano-cable that described C coats, obtain the Te nano-cable aqueous solution of 5g/L;
In the 100mLTe nano-cable aqueous solution, add the hydrochloric acid of 100mL0.5mol/L and the hydrogen peroxide of 100mL0.5mol/L, behind the stirring reaction, will obtain carbon nano-fiber after reactant mixture centrifugation, washing, the drying.
Described carbon nano-fiber is carried out field emission scanning electron microscope to be observed, the result is referring to Fig. 8, the stereoscan photograph of the carbon nano-fiber that Fig. 8 provides for the embodiment of the invention 5, as shown in Figure 8, it is comparatively even that the present invention obtains the diameter of carbon nano-fiber, for about 195nm, its length is longer, can reach tens microns.
Described carbon nano-fiber vigorous stirring is scattered in the water, obtains the slurry of 8g/L; The described slurry of 6mL evenly is applied in the polytetrafluoroethylene (PTFE) circular trough that internal diameter is 5cm, and at room temperature air dry 24h peels off described carbon nano-fiber from described ptfe surface, obtains the carbon nano-fiber film.
Described carbon nano-fiber film can be peeled off from ptfe surface, but and stable existence, it has good pliability and mechanical stability, has certain self-supporting function.
Described carbon nano-fiber film is carried out field emission scanning electron microscope observe, the result shows that it is comparatively even that the present invention obtains carbon nano-fiber film surface, and no aperture, slight crack or other defect exist.
Described carbon nano-fiber film is carried out the contact angle test, and its contact angle is 0 °, and contact angle is lower, has Superhydrophilic, can be used as filter membrane and uses.
Embodiment 6
With 1g polyvinylpyrrolidone and 92mg Na
2TeO
3Join in the 32mL water, after stirring, add 1.67mL hydrazine hydrate and 3.33mL ammoniacal liquor again, be stirred to phase-splitting and evenly be placed in the airtight container, be warming up to 180 ℃ of reaction 3h, obtain the Te nano wire, regulate the concentration of Te nano wire, obtain the Te nano wire aqueous solution of 0.18g/L;
The described Te nano wire of the 100mL aqueous solution is mixed with the D/W of 100mL67g/L, stir and be placed in the closed container, carry out the hydrothermal carbonization reaction under 160 ℃, behind the reaction 72h, be cooled to room temperature, obtain the Te nano-cable that C coats, regulate the Te nano-cable that described C coats, obtain the Te nano-cable aqueous solution of 5g/L;
In the 100mLTe nano-cable aqueous solution, add the hydrochloric acid of 100mL0.5mol/L and the hydrogen peroxide of 100mL0.5mol/L, behind the stirring reaction, will obtain carbon nano-fiber after reactant mixture centrifugation, washing, the drying.
Described carbon nano-fiber is carried out field emission scanning electron microscope to be observed, the result is referring to Fig. 9, the stereoscan photograph of the carbon nano-fiber that Fig. 9 provides for the embodiment of the invention 6, as shown in Figure 9, it is comparatively even that the present invention obtains the diameter of carbon nano-fiber, for about 280nm, its length is longer, can reach tens microns.
Described carbon nano-fiber vigorous stirring is scattered in the water, obtains the slurry of 8g/L; The described slurry of 6mL evenly is applied in the polytetrafluoroethylene (PTFE) circular trough that internal diameter is 5cm, and at room temperature air dry 24h peels off described carbon nano-fiber from described ptfe surface, obtains the carbon nano-fiber film.
Described carbon nano-fiber film can be peeled off from ptfe surface, but and stable existence, it has good pliability and mechanical stability, has certain self-supporting function.
Described carbon nano-fiber film is carried out field emission scanning electron microscope observe, the result shows that it is comparatively even that the present invention obtains carbon nano-fiber film surface, and no aperture, slight crack or other defect exist.
Described carbon nano-fiber film is carried out the contact angle test, and its contact angle is 0 °, and contact angle is lower, has Superhydrophilic, can be used as filter membrane and uses.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of a carbon nano-fiber film may further comprise the steps:
A) tellurium nano-wire is mixed in the aqueous solution with glucose, carry out obtaining carbon coating tellurium nano-cable after the carburizing reagent;
B) coat adding hydrochloric acid and hydrogen peroxide in the tellurium nano-cable to described carbon, carry out obtaining carbon nano-fiber after the oxidation reaction;
C) described carbon nano-fiber is scattered in obtains slurry in the solvent, described slurry is applied on the backing material, obtain the carbon nano-fiber film after the drying.
2. preparation method according to claim 1 is characterized in that, in the described step a), the mass ratio of described tellurium nano-wire and described glucose is (0.10～0.20): (60～70).
3. preparation method according to claim 1 is characterized in that, in the described step a), the temperature of described carburizing reagent is 160 ℃～220 ℃.
4. preparation method according to claim 1 is characterized in that, in the described step a), the time of described carburizing reagent is 15h～80h.
5. preparation method according to claim 1, it is characterized in that, in the described step b), the ratio that described carbon coats the amount of substance of the amount of substance of the quality of tellurium nano-cable, described hydrochloric acid and described hydrogen peroxide is (3g～8g): (0.2mol～0.8mol): (0.2mol～0.8mol).
6. preparation method according to claim 1 is characterized in that, in the described step c), described solvent is water or ethanol.
7. preparation method according to claim 1 is characterized in that, in the described step c), the ratio of the quality of described carbon nano-fiber and the volume of described solvent is (5g～10g): 1L.
8. preparation method according to claim 1 is characterized in that, in the described step c), described backing material is a polytetrafluoroethylene (PTFE).
9. according to any described preparation method of claim 1～8, it is characterized in that in the described step a), described tellurium nano-wire prepares in accordance with the following methods:
Polyvinylpyrrolidone, sodium tellurite, hydrazine hydrate and ammoniacal liquor are mixed in the aqueous solution, obtain tellurium nano-wire after the reaction.
10. preparation method according to claim 9 is characterized in that, the temperature of described reaction is 160 ℃～200 ℃, and the time of described reaction is 3h～5h.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935638A (en) * | 2005-09-23 | 2007-03-28 | 中国科学技术大学 | Method for preparing carbon nano fiber |
-
2011
- 2011-03-29 CN CN2011100776042A patent/CN102179182A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935638A (en) * | 2005-09-23 | 2007-03-28 | 中国科学技术大学 | Method for preparing carbon nano fiber |
Non-Patent Citations (1)
| Title |
|---|
| HAI-WEI LIANG ET AL.: "Carbonaceous Nanofiber Membranes for Selective Filtration and Separation of Nanoparticles", 《ADV.MATER.》 * |
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