Summary of the invention
For addressing the above problem, the object of the present invention is to provide a kind of CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material and preparation method thereof, the Co of the CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material of preparing by the method
3o
4particle is cube, and evenly, the length of side is less than 7nm to size, has each other certain space, is about 1-10nm, is evenly distributed on CNT (carbon nano-tube) surface.
For achieving the above object, technical scheme of the present invention is:
A preparation method for CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material, comprises the following steps:
The ratio of taking is 1: 1-1: 9 deionized water and dimethyl formamide DMF, obtain mixed solvent after mixing and stirring;
Take purified CNT (carbon nano-tube) after treatment and mixed solvent by the matched proportion density of 0.1-1g/L, CNT (carbon nano-tube) is put into mixed solvent and carry out ultrasonic 10-60 minute, obtain CNT (carbon nano-tube) dispersion liquid;
Take four hydration cobalt acetates, cobalt is II valency, and wherein four hydration cobalt acetates are 10-60g/L with respect to the concentration of CNT (carbon nano-tube) dispersion liquid, and four hydration cobalt acetates are dissolved in to CNT (carbon nano-tube) dispersion liquid, stirs;
Above mixed solution is put into the hydro-thermal tank with tetrafluoroethene liner, wherein the filling volume ratio of hydro-thermal tank is 1/5-1/2, is warmed up to 100-150 DEG C with the programming rate of 1 DEG C/min-10 DEG C/min, and temperature retention time is 1.5h-10h, after cooling with stove;
After cool to room temperature, solution is poured out, black deposit is cleaned with centrifuge, cleaning fluid adopts alcoholic solution, and the number of times of cleaning is at 3-5 time;
The black deposit having cleaned is baked to sample drying at 40-80 DEG C, obtains CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material.
Preferably, the concrete purification step of purified CNT (carbon nano-tube) after treatment is: the carbon nano-tube that 0.5g chemical vapour deposition (CVD) CVD method is prepared joins in 100ml red fuming nitric acid (RFNA), first ultrasonic dispersion 30min, after add hot reflux 4h, remove the catalyst granules in carbon nano-tube and connect corresponding functional group in carbon nano tube surface, mixture cooled and filtered, cleans until filtrate is neutral dry 6h at 100 DEG C in air repeatedly with deionized water.
And, a kind of CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material, described CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material is prepared by method as previously discussed, and cobaltosic oxide material becomes nano cubic even structure to be attached to the surface of CNT (carbon nano-tube).
Preferably, the size of described nano cubic structure is less than 7nm, Co
3o
4gap between nano cubic particle is 1-10nm.
Compared with prior art, beneficial effect of the present invention is as follows:
(1) Co of carbon nano tube surface
3o
4nano particle is evenly distributed, this Co
3o
4particle advantages of good crystallization, is isometric particle, and evenly, the length of side is less than 7nm to size, has each other even space, is about 1-10nm, is evenly distributed on the surface of CNT (carbon nano-tube);
(2) CNT (carbon nano-tube) has larger specific area, good conductivity and thermal conduction characteristic, carbon nano-tube and Co
3o
4particle close contact, is conducive to the fast transport of electronics.
(3) CNT (carbon nano-tube) and cobaltosic oxide nano Interaction between particles, has avoided the accumulation again of carbon pipe and the reunion of oxide nano particles.
(4) this method preparation process is simple and controlled and repeatable good, is suitable for volume production.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
On the contrary, the present invention contain any defined by claim in marrow of the present invention and scope, make substitute, amendment, equivalent method and scheme.Further, for the public is had a better understanding to the present invention, in below details of the present invention being described, detailed some specific detail sections of having described.Do not have for a person skilled in the art the description of these detail sections can understand the present invention completely yet.
Referring to Fig. 1, be depicted as the preparation method's of a kind of CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material of the embodiment of the present invention flow chart of steps, it comprises the following steps:
S10, the ratio of taking is 1: 1-1: 9 deionized water and dimethyl formamide DMF, obtain mixed solvent after mixing and stirring;
S20, takes purified CNT (carbon nano-tube) after treatment and mixed solvent by the matched proportion density of 0.1-1g/L, CNT (carbon nano-tube) is put into mixed solvent and carry out ultrasonic 10-60 minute, obtains CNT (carbon nano-tube) dispersion liquid;
Wherein, in concrete application example, the concrete purification step of CNT (carbon nano-tube) can be, the carbon nano-tube that 0.5g chemical vapour deposition (CVD) CVD method is prepared joins in 100ml red fuming nitric acid (RFNA), first ultrasonic dispersion 30min, after add hot reflux 4h, remove the catalyst granules in carbon nano-tube and connect corresponding functional group in carbon nano tube surface, mixture cooled and filtered, cleans until filtrate is neutral dry 6h at 100 DEG C in air repeatedly with deionized water.
S30, takes four hydration cobalt acetates, and cobalt is II valency, and wherein four hydration cobalt acetates are 10-60g/L with respect to the concentration of CNT (carbon nano-tube) dispersion liquid, and four hydration cobalt acetates are dissolved in to CNT (carbon nano-tube) dispersion liquid, stirs;
In concrete application example below, be that four hydration cobalt acetates of II valency are referred to as four hydration cobalt acetates (II) by cobalt.
S40, above mixed solution is put into the hydro-thermal tank with tetrafluoroethene liner, wherein the filling volume ratio of hydro-thermal tank is 1/5-1/2, be the 20%-50% that reaction solution volume accounts for hydro-thermal tank cumulative volume, programming rate with 1 DEG C/min-10 DEG C/min is warmed up to 100-150 DEG C, temperature retention time is 1.5h-10h, after cooling with stove;
S50, after cool to room temperature, pours out solution, black deposit is cleaned with centrifuge, and cleaning fluid adopts alcoholic solution, and the number of times of cleaning is at 3-5 time;
S60 is baked to sample drying by the black deposit having cleaned at 40-80 DEG C, obtains CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material.
Known by above preparation process explanation, the present invention adopts above method to prepare carbon nano tube surface loaded with nano cobaltosic oxide composite material, and preparation process is simple and controlled and repeatable good, is suitable for volume production.
Therefore, corresponding with method, further embodiment of this invention provides the carbon nano tube surface loaded with nano cobaltosic oxide of preparing by said method composite material, referring to Fig. 2 to Fig. 5, Fig. 2 and Fig. 3 are respectively the scanning electron microscope (SEM) photograph of carbon nano tube surface loaded with nano cobaltosic oxide composite material prepared by the embodiment of the present invention, Fig. 4 is transmission electron microscope picture, and Fig. 5 is XRD figure.From Fig. 2 to Fig. 4, cobaltosic oxide material becomes nano cubic even structure to be attached to the surface of CNT (carbon nano-tube), and the size of nano cubic structure is less than 7nm, Co
3o
4gap between nano cubic particle is 1-10nm.Referring to Fig. 5, in X-ray diffraction, can obviously see (002) diffraction maximum of CNT (carbon nano-tube).
To the preparation process of CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material be described by multiple specific embodiments below.The hydro-thermal tank using in specific embodiment is market and buys, and its typical volume is 20ml, 50ml, 100ml and 250ml.In specific embodiment, the cumulative volume of mixed solution can cover reaction solution volume and account for the 20%-50% of hydro-thermal tank cumulative volume in the adjustment of proportioning ratio.
Embodiment 1
Take DMF8ml, deionized water 2ml, stirs, and obtains mixed solvent.Take the CNT (carbon nano-tube) 4mg after purification process, CNT (carbon nano-tube) is put into mixed solvent and carry out ultrasonic 60 minutes, obtain CNT (carbon nano-tube) dispersion liquid.Take four hydration cobalt acetate (II) 400mg, four hydration cobalt acetates (II) are dissolved in and obtain CNT (carbon nano-tube) dispersion liquid, be stirred to completely and dissolve.Above solution is put into and had the hydro-thermal tank that the volume of tetrafluoroethene liner is 20ml, the cumulative volume that reaction solution accounts for hydro-thermal tank is about 50%, meets the filling volume proportion requirement of hydro-thermal tank, is warmed up to 120 DEG C with the programming rate of 1 DEG C/point, temperature retention time 1.5h, after cooling with stove.Microparticle is cleaned with centrifuge, clean and adopt alcoholic solution, the number of times of cleaning is at 5 times.At 40 DEG C, be baked to sample drying, obtain CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material.
Embodiment 2
Take DMF10ml, deionized water 10ml, stirs, and obtains solvent.Take the carbon nano-tube 2mg after purification process, CNT (carbon nano-tube) is put into solvent and carry out ultrasonic 10 minutes, obtain CNT (carbon nano-tube) dispersion liquid.Take four hydration cobalt acetate (II) 200mg, four hydration cobalt acetates (II) are dissolved in to mixed solvent, be stirred to completely and dissolve.Above solution is put into and had the hydro-thermal tank that the volume of tetrafluoroethene liner is 50ml, the cumulative volume that reaction solution accounts for hydro-thermal tank is about 40%, meets the filling volume proportion requirement of hydro-thermal tank, is warmed up to 150 DEG C with the programming rate of 5 DEG C/point, temperature retention time 5h, after cooling with stove.Microparticle is cleaned with centrifuge, clean and adopt alcoholic solution, the number of times of cleaning is at 3 times.At 80 DEG C, be baked to sample drying, obtain CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material.
Embodiment 3
Take DMF27ml, deionized water 3ml, stirs, and obtains solvent.Take the carbon nano-tube 30mg after purification process, carbon nano-tube is put into solvent and carry out ultrasonic 40 minutes, obtain CNT (carbon nano-tube) dispersion liquid.Take four hydration cobalt acetate (II) 1800mg, four hydration cobalt acetates (II) are dissolved in to mixed solvent, be stirred to completely and dissolve.Above solution is put into and had the hydro-thermal tank that the volume of tetrafluoroethene liner is 100ml, the cumulative volume that reaction solution accounts for hydro-thermal tank is about 30%, meets the filling volume proportion requirement of hydro-thermal tank, is warmed up to 130 DEG C with the programming rate of 10 DEG C/point, temperature retention time 10h, after cooling with stove.Microparticle is cleaned with centrifuge, clean and adopt alcoholic solution, the number of times of cleaning is at 5 times.At 60 DEG C, be baked to sample drying, obtain CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material.
Embodiment 4
Take DMF40ml, deionized water 10ml, stirs, and obtains solvent.Take the carbon nano-tube 30mg after purification process, carbon nano-tube is put into solvent and carry out ultrasonic 30 minutes, obtain CNT (carbon nano-tube) dispersion liquid.Take four hydration cobalt acetate (II) 1000mg, four hydration cobalt acetates (II) are dissolved in to mixed solvent, be stirred to completely and dissolve.Above solution is put into the hydro-thermal tank that volume is 250ml, and the cumulative volume that reaction solution accounts for hydro-thermal tank is about 20%, meets the filling volume proportion requirement of hydro-thermal tank, is warmed up to 140 DEG C with the programming rate of 5 DEG C/point, temperature retention time 4h, after cooling with stove.Microparticle is cleaned with centrifuge, clean and adopt alcoholic solution, the number of times of cleaning is at 4 times.At 40 DEG C, be baked to sample drying, obtain CNT (carbon nano-tube) area load nano-cobaltic-cobaltous oxide composite material.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.