CN102965766B - New method for synthesizing nanometal particle-loaded carbon nanofiber - Google Patents
New method for synthesizing nanometal particle-loaded carbon nanofiber Download PDFInfo
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Abstract
The invention relates to a new method for synthesizing nanometal particle-loaded carbon nanofiber. According to the method, an iron-containing compound and a high molecular polymer are taken as reaction precursors and the method comprises the following steps of: mixing the reaction precursors, absolute ethyl alcohol and dimethylformamide (DMF) to obtain a uniform solution; preparing pre-composite nanofiber by an electrostatic spinning device, and drying; transferring the nanofiber into a tube furnace; heating to 500-700 DEG C in oxygen-free condition; and keeping the temperature for a certain period of time to obtain the nanometal particle-loaded carbon nanofiber. Compared with the prior art, the method provided by the invention takes short time and has simple steps.
Description
Technical field
The invention belongs to technical field of nano material, relate to a kind of new method of synthesis of nano metallic particles load carbon nano-fiber.
Background technology
Carbon nano-fiber (CNF) has as one-dimensional nano structure material and has similar surface chemistry to CNT, high mechanical strength, good electric conductivity and large specific area, it not only has the skin effect that usual nano material has, quantum size effect and small-size effect etc., also there is excellent heat endurance, mechanical property, electronics and photon transmission, optical property and photoconductivity can wait, make it can as the basic construction unit of material, at nanometer electricity and optics, sensor, the aspects such as nanometer biotechnology demonstrate important using value.The method of constructing monodimension nanometer material mainly contains template (template-assisted), gas-liquid-solid reaction method (vapaor-liquid-solid), vapor-solid growth method (apaor--solid), hydro-thermal method (hydrothermal synthesis), method of electrostatic spinning (elctrospinnning) etc.In these methods, method of electrostatic spinning is simple with its manufacturing installation, spinning is with low cost, can spin the advantages such as substance classes is various, technique is controlled, has become effectively one of main path preparing nano-fiber material.Electrostatic spinning technique has been successfully applied to prepares polymer, pottery, metal and inorganic/organic composite fiber.
Iron is active metal, has reducibility.Nanometer metallic iron, due to its application increasingly extensive in high magnetic recording density material, magnetic material, catalyst material, electric conductor and the field such as electromagnetic wave absorbent material and biomedical carrier material, is more and more subject to the attention of researcher in recent years to the research of nanometer metallic iron.Carbon-coated magnetic nano particle, as Fe, Co, Ni, owing to there being the protection of carbon, makes it in magnetic data storage, xerography, magnetic ink, magnetic fluid and bioengineering (administration, magnetic resonance etc.), have application.
Method of electrostatic spinning is adopted to prepare carbon nano-fiber (Fe/CNF) composite of Fe nano particle load herein.Have about the method preparing Fe@C composite in document disclosed in prior art: chemical vapour deposition technique, arc discharge method, high-temperature catalytic decomposition method etc.The Fe@C core shell structure compound that utilized arc discharge method to prepare such as Jiao J, but the method yields poorly, temperature is high.Song H H utilizes chemical vapour deposition technique also to prepare Fe@C compound, but the method needs independently carbon source, catalyst, catalyst difficulty and separation of products.In the Fe@C compound of these methods synthesis, iron nano-particle is all coated on inside material with carbon element and is not fully used.
Summary of the invention
Object of the present invention is exactly the defect existed to overcome existing technology of preparing, and provides a kind of new electrospinning process to prepare nano-metal particle load carbon nano-fiber.
Object of the present invention can be achieved through the following technical solutions:
The present invention relates to a kind of new method of synthesis of nano metallic particles load carbon nano-fiber, it is characterized in that, the method is using ferrocene and high molecular polymer as pre-reaction material, pre-reaction material, absolute ethyl alcohol and dimethyl formamide (DMF) three are mixed to form homogeneous solution, adopt electrostatic spinning apparatus composite nano fiber in obtained early stage, drying, nanofiber proceeds in tube furnace, be heated to 500-700 DEG C in the absence of oxygen, and be incubated the carbon nano-fiber that a period of time can obtain nano-metal particle load at such a temperature.
The reaction system of the simple raw material of above-mentioned utilization, simple mechanism and easy steps, the method specifically comprises the following steps:
(1) ferrocene and high molecular polymer are dissolved in the mixed solvent of a certain proportion of absolute ethyl alcohol and dimethyl formamide and are mixed with certain density solution, this solution needs magnetic agitation a few hours to form uniform solution, wherein the mass ratio of ferrocene and high molecular polymer is 9:25--5:6, the volume ratio of absolute ethyl alcohol and dimethyl formamide is 1:1--0:1, and the mass ratio of high molecular polymer and mixed solvent is 2:17--2:31.
(2) mixed solution step (1) obtained moves in syringe, carries out electrostatic spinning with certain voltage, spinning speed and receiving range, and setting syringe pump, high pressure generator control program make whole spinning process continue some hours.After spinning terminates, gained fiber is dry under 55--65 DEG C of condition, and this product is composite nano fiber in early stage.
(3) product that step (2) obtained moves in tube furnace, is heated to 500-700 DEG C, and keeps a period of time at such a temperature in argon atmosphere with certain heating rate.After reaction stops, naturally cooling, obtaining end product is black nano metallic particles load carbon nano-fiber.
Preferably, described pbz polymer polymer is polyvinylpyrrolidone or polyacrylonitrile.
Preferably, the certain spinning condition described in step (2) is the receiving range of the voltage of 10-13Kv, the flow velocity of 0.5-1ml/h and 10-20cm.
Preferably, the heating rate described in step (3) and temperature retention time are respectively 1-2 DEG C/min and 1-2h.
Mechanism of the present invention: there is organo-metallic compound ferrocene in the precursor used in this invention, the catalyst that this material not only can be prepared as carbon nano-fiber, simultaneously itself can also as carbon source, that is: electrostatic spinning technique is adopted, ferrocene is dispersed in the nanofiber of high molecular polymer uniformly, improve high molecular polymer catalytic effect, again in conjunction with the high-temperature heating under follow-up oxygen free condition, high molecular polymer is carbonized, ferrocene is decomposed simultaneously, luxuriant ring wherein also forms carbon nano-fiber as carbon source, and ferro element assembles formation nano iron particles at carbon fiber surface.
The bright method of electrostatic spinning of we not only simplifies synthesis step, there is not being separated of product and catalyst, and the Fe@C compound obtained is one dimension size simultaneously.Compared with prior art, the inventive method is simple, raw material is easy to get, equipment is simple, easy to operate, and can prepare the nano-metal particle load carbon nano-fiber of size uniformity, preparation cost reduces greatly.
In carbon nano-fiber (Fe/CNF) composite of the Fe nano particle load that the present invention adopts method of electrostatic spinning to prepare, nano iron particles is that load is on carbon nano-fiber surface, instead of being coated on inside material with carbon element, such combining structure makes the character of Fe@C compound be more suitable for being applied to the field such as catalyst material, electrode material.
Accompanying drawing explanation
Fig. 1 be embodiment 1 early stage combination product scanning electron microscope (SEM) photograph.
Fig. 2 is the scanning electron microscope (SEM) photograph of the end product of embodiment 1.
Fig. 3 is end product transmission electron microscope picture in embodiment 1.
Fig. 4 is end product transmission electron microscope picture in embodiment 1.
Fig. 5 is the scanning electron microscope (SEM) photograph of the end product of embodiment 2.
Fig. 6 is the scanning electron microscope (SEM) photograph of the end product of embodiment 3
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.The all raw materials participating in reaction system in embodiment are commercially available; polyvinylpyrrolidone (MW=1300000) is bought in Aldrich; polyacrylonitrile (MW=150000) is bought in J & K Science and Technology Ltd.; ferrocene is purchased from Brassica rapa L and analyses Chemical Industry Science Co., Ltd; dimethyl formamide and ethanol are all purchased from Solution on Chemical Reagents in Shanghai company of Chinese Medicine group; it is pure that above chemical reagent is analysis, not purified direct use.
Embodiment 1
The first step, takes 2.0g polyvinylpyrrolidone and 0.9g ferrocene is dissolved in beaker, adds 11ml absolute ethyl alcohol and 9ml solvent dimethylformamide, is placed in magnetic agitation in beaker and forms even orange solution.
Second step, proceeds in syringe by the solution prepared, connects electrostatic spinning apparatus, arrange spinning condition, and voltage is 13Kv, and injection rate is 1ml/h receiving range is 15cm.Start high pressure generator, spinning process continues 5 hours, then that obtained composite nano fiber is dry under 60 ° of C.To in earlier stage peel off by combination product from aluminium foil with tweezers, by field emission scanning electron microscope (Philips company, XL-30E, SEM), setting scanning voltage 3KV, can find out under multiplication factor 60,000 times of (Fig. 1) conditions, early stage, combination product was one dimension linear structure, but surface there is no particulate load.
3rd step, proceeds in tube furnace by second step product, directly in argon atmosphere, is heated to 500 ° of C with the speed of 2 ° of C/min, and is incubated 1h at these 500 ° of C temperature, then naturally cools to room temperature.Now the product of gained is nano-metal particle load carbon nano-fiber.And sample is analyzed:
(1) by field emission scanning electron microscope (Philips company, XL-30E, SEM), setting scanning voltage 3KV, can find out under multiplication factor 20,000 times of (Fig. 2) conditions, product is one dimension linear structure, and has metallic particles load at fiber surface.In figure, a indicates ferrous metal particle, and b indicates carbon nano-fiber.
(2) by transmission electron microscope (JEOL company, JEM-2100, TEM), under setting scale 100nm condition, (Fig. 3) can find out, metallic particles is evenly embedded in carbon nano-fiber surface, and such particle is not easy to split away off.
(3) by transmission electron microscope Electronic Speculum (JEOL company, JEM-2100, TEM), under setting scale 5nm condition (Fig. 4), can see interplanar distance, known metallic particles is the good monocrystalline of crystallinity.
Embodiment 2
The first step, takes 1.0g polyacrylonitrile and 0.5g ferrocene is dissolved in beaker, and add 10ml solvent dimethylformamide, magnetic agitation forms even orange solution.
Second step, proceeds in syringe by the solution prepared, connects electrostatic spinning apparatus, arrange spinning condition, and voltage is 10Kv, and injection rate is 0.5ml/h receiving range is 19cm.Start high pressure generator, spinning process holds 5 hours, then that obtained composite nano fiber is dry under 61 ° of C. peel off product and aluminium foil with tweezers.
3rd step, proceeds in tube furnace by second step product, in air atmosphere encloses, be heated to 250 ° of C with the speed of 2 ° of C/min, and insulation 0.5h. continues to be heated to 700 ° of C again in argon atmosphere at such a temperature, and insulation 1h, then naturally cools to room temperature.Now the product of gained is nano-metal particle load carbon nano-fiber.
The present embodiment sample is analyzed: by field emission scanning electron microscope (Philips company, XL-30E, SEM), setting scanning voltage is 3KV, multiplication factor is that under 30,000 times of conditions, (Fig. 5) can clearly find out, product is one dimension linear structure, and has metallic particles load at fiber surface.
Embodiment 3
The first step, takes 1.5g polyvinylpyrrolidone and 0.6g ferrocene is dissolved in beaker, adds 9ml absolute ethyl alcohol and 6ml solvent dimethylformamide, is placed in magnetic agitation in beaker and forms even orange solution.
Second step, proceeds in syringe by the solution prepared, connects electrostatic spinning apparatus, arrange spinning condition, and voltage is 11Kv, and injection rate is 0.6ml/h receiving range is 17cm.Start high pressure generator, spinning process continues 10 hours, then that obtained composite nano fiber is dry under 64 ° of C. peel off product and aluminium foil with tweezers.
3rd step, proceeds in tube furnace by second step product, directly in argon atmosphere, is heated to 600 ° of C with the speed of 1 ° of C/min, and is incubated 2h at such a temperature, then naturally cool to room temperature.Now the product of gained is nano-metal particle load carbon nano-fiber.
The present embodiment sample is analyzed: by field emission scanning electron microscope (Philips company, XL-30E, SEM), setting scanning voltage is 3KV, multiplication factor is that under 60,000 times of conditions, (Fig. 6) can clearly find out, product presents one dimension linear structure equally, and has metallic particles load on carbon nano-fiber surface.
Claims (4)
1. one kind is applied to the new method of the synthesis of nano metallic particles load carbon nano-fiber in catalyst material and electrode material field, it is characterized in that, the method is using ferrocene and high molecular polymer as pre-reaction material, by pre-reaction material, absolute ethyl alcohol and dimethyl formamide three are mixed to form homogeneous solution, adopt electrostatic spinning apparatus composite nano fiber in obtained early stage, drying, nanofiber proceeds in tube furnace, be heated to 500 DEG C in the absence of oxygen, and under this outlet temperature, be incubated the carbon nano-fiber that a period of time can obtain nano-metal particle load.
2. the method for claim 1, is characterized in that, the method specifically comprises the following steps:
(1) ferrocene and high molecular polymer are dissolved in the mixed solvent of a certain proportion of absolute ethyl alcohol and dimethyl formamide and are mixed with certain density solution, this solution needs to stir the uniform solution of formation, wherein the mass ratio of ferrocene and high molecular polymer is 9:25--5:6, the volume ratio of absolute ethyl alcohol and dimethyl formamide is 1:1--0:1, and the mass ratio of high molecular polymer and mixed solvent is 2:17--2:31;
(2) mixed solution step (1) obtained moves in syringe, electrostatic spinning is carried out with certain voltage, spinning speed and receiving range, setting syringe pump, high pressure generator control program make whole spinning process continue some hours, after spinning terminates, gained fiber is dry under 55--65 DEG C of condition, and this product is composite nano fiber in early stage;
(3) product step (2) obtained moves in tube furnace, 500 DEG C are heated to certain heating rate in argon atmosphere, and a period of time is kept under this outlet temperature, after reaction stops, naturally cool, obtaining end product is black nano metallic particles load carbon nano-fiber.
3. method as claimed in claim 2, it is characterized in that, carry out electrostatic spinning with certain voltage, spinning speed and receiving range described in step (2), its concrete spinning condition is the receiving range of the voltage of 10-13Kv, the flow velocity of 0.5-1ml/h and 10-20cm.
4. method as claimed in claim 2, is characterized in that, is heated to 500 DEG C described in step (3), and its heating rate is 1-2 DEG C/min, is 1-2h in the temperature retention time of this outlet temperature.
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