Micro-nano structure zinc oxide-carbon compound ball and preparation method thereof
Technical field
The present invention relates to a kind of compound ball and preparation method, especially a kind of micro-nano structure zinc oxide-carbon compound ball and preparation method thereof.
Background technology
Zinc oxide is the semiconductor material that a class is good, is having application very widely aspect environmental improvement and opto-electronic device; Photocatalysis performance as good in it can even be degraded into carbonic acid gas and water by toxic organic pollutant under the irradiation of daylight in UV-light, utilize its good piezoelectric property can be made nano generator device, its good opto-electronic conversion performance can make it be applied on a large scale in solar cell.There is the carbon material of excellent conductive capability and absorption property, all have a wide range of applications at photoelectricity and Chu Qing field.Based on above 2 points, in the recent period, people are in order to obtain zinc oxide-carbon composite, make unremitting effort, as disclosed a kind of ZnO-carbosphere and its preparation method 26th~27 pages of " carbon, the preparation of ZnO/ carbon porous microsphere and the applied research on lithium ion battery negative thereof " (Chinese excellent MA theses full-text database o. 11th, Cao Yang) literary compositions.The spherical diameter of the ZnO-carbosphere of mentioning in this article is 300nm~3 μ m, and surface and inside that its spherical ZnO uniform particles that is 80nm by diameter is distributed in carbosphere form, and having bore dia on the surface of carbosphere is the hole defect of receiving of 5~10nm; Preparation method for first by glucose crystal and zinc acetate ultrasonic dissolution in distilled water, obtain clear solution, again clear solution is placed in to air-tight state, at 180 DEG C, react 12~18h, obtain the reaction product of brown or black particle, through to its centrifugation, repeatedly wash and be dried after, be placed under argon atmospher in 500 DEG C of high temperature annealing 2h, obtain final product--ZnO-carbosphere.But, no matter be final product, or its preparation method, there is shortcoming part, first, though hole defect is received on the surface of ZnO-carbosphere, too smooth also, make its difficulty have larger specific surface area; Secondly, have obvious interface between Zinc oxide particles and carbosphere, this illustrates that the tightness of both combinations is not too desirable; Finally, temperature of reaction in preparation method is higher, overlong time, and temperature when annealing is also higher, makes it both when energy charge, can not obtain again the final product of high specific surface area.
Summary of the invention
The technical problem to be solved in the present invention, for overcoming shortcoming part of the prior art, provides one to have high specific surface area, constitutionally stable micro-nano structure zinc oxide-carbon compound ball.
Another technical problem that the present invention will solve is for providing a kind of preparation method of above-mentioned micro-nano structure zinc oxide-carbon compound ball.
For solving technical problem of the present invention, the technical scheme adopting is: micro-nano structure zinc oxide-carbon compound ball forms solid sphere by zinc oxide and carbon, particularly,
Described solid sphere is formed by zinc oxide and carbon hybridization compounding, and its spherical diameter is 6~12 μ m, the nanometer sheet of ball surface for standing;
The length of a film of described nanometer sheet is the high 700~900nm of being of 700~900nm, sheet, the thick 15~25nm of being of sheet, between sheet and sheet, is interconnected to nest;
The molar percentage of described zinc oxide and carbon is 60~70%: 30~40%, and wherein, zinc oxide is six side's phase structures, and carbon is amorphous carbon and graphitized carbon, and the weight percent of described amorphous carbon and graphitized carbon is 85~95wt%: 5~15wt%.
As the further improvement of micro-nano structure zinc oxide-carbon compound ball, described nest is Polygons; Described Polygons is trilateral, or tetragon, or sexangle.
For solving another technical problem of the present invention, another technical scheme adopting is: the preparation method of above-mentioned micro-nano structure zinc oxide-carbon compound ball comprises hydrothermal method, and particularly completing steps is as follows:
Step 1, be first 0.64~0.68: 0.52~0.56 according to the weight ratio between two hydration zinc acetates, urea, two hydration Trisodium Citrates, glucose and water: 0.05~0.07: 0.8~1.2: 48~52 ratio, two hydration zinc acetates, urea, two hydration Trisodium Citrates and glucose are dissolved in the water, obtain mixed solution, again mixed solution is placed in to air-tight state, be at 120~160 DEG C, to react at least 2h in temperature, obtain reaction solution;
Step 2, first carries out solid-liquid separation, washing and dry processing successively to reaction solution, obtains intermediate product, then intermediate product is placed in to inert gas atmosphere, and at least 1h that anneals at 300~400 DEG C, makes micro-nano structure zinc oxide-carbon compound ball.
As the preparation method's of micro-nano structure zinc oxide-carbon compound ball further improvement, described solid-liquid separation is treated to centrifugation, and rotating speed when separation is 3000~5000r/min; Described carrying out washing treatment is for being used deionized water and ethanol to clean; Described drying treatment for to dry at 10~50 DEG C; Described is rare gas element is in nitrogen, argon gas, helium one or more mixed gas.
Beneficial effect with respect to prior art is, one, uses respectively scanning electron microscope, transmission electron microscope, X-ray diffractometer and Raman spectrometer to characterize to the target product making, and from its result, target product is the stand solid sphere of nanometer sheet of its surface; Wherein, the spherical diameter of solid sphere is 6~12 μ m, and the length of a film of nanometer sheet is the high 700~900nm of being of 700~900nm, sheet, the thick 15~25nm of being of sheet, between sheet and sheet, is interconnected to nest.Target product is formed by zinc oxide and carbon hybridization compounding; The molar percentage of zinc oxide and carbon is 60~70%: 30~40%, and zinc oxide is wherein six side's phase structures, and carbon is amorphous carbon and graphitized carbon, and the weight percent of amorphous carbon and graphitized carbon is 85~95wt%: 5~15wt%.They are two years old, preparation method's science, effective, both energy-and time-economizing, be beneficial to commercial scale production, make again the target product making have higher specific surface area, also contain a large amount of functional groups because of carbon surface and make zinc oxide and carbon very tight in conjunction with obtaining after hybridization compounding, greatly improved the stability of its structure, more because the existence of a large amount of functional groups in carbon surface makes target product have potential application prospect in absorption and catalytic field.
As the further embodiment of beneficial effect, the one, nest is preferably Polygons, and Polygons is preferably trilateral, or tetragon, or sexangle, is beneficial to leaning on each other for support between nanometer sheet, has improved the stability that nanometer sheet is stood.The 2nd, solid-liquid separation processing is preferably centrifugation, and rotating speed when separation is preferably 3000~5000r/min, is convenient to the effective separation between solid-liquid.The 3rd, carrying out washing treatment is preferably and uses deionized water and ethanol to clean, and has ensured the pure of intermediate product.The 4th, drying treatment is preferably at 10~50 DEG C dries, and has guaranteed the quality of intermediate product.The 5th, rare gas element is preferably one or more the mixed gas in nitrogen, argon gas, helium, not only makes the source of raw material compared with horn of plenty, also makes preparation technology more easily implement and flexibly.
Brief description of the drawings
Below in conjunction with accompanying drawing, optimal way of the present invention is described in further detail.
Fig. 1 is that target product to making uses one of result that scanning electron microscope (SEM) characterizes.Wherein, the low range SEM photo that Fig. 1 a is target product, Fig. 1 b is the high magnification photo of Fig. 1 a, Fig. 1 c is the high magnification photo of Fig. 1 b, can be found out by Fig. 1 b and Fig. 1 c, and target product is globe, its surface a large amount of nanometer sheet of standing, is interconnected to nest between nanometer sheet; Fig. 1 d is the EDS spectrogram obtaining after using subsidiary power spectrum (EDS) test component of scanning electron microscope to characterize to the target product shown in Fig. 1 a, can find out that by EDS spectrogram target product contains zinc, oxygen and three kinds of elements of carbon, wherein, the ratio of Zn and 0 relative atom molar content is approximately 1: 1, for the structure of ZnO, the atomic molar content of C is about 30~40%.
Fig. 2 is that target product to making uses one of result that transmission electron microscope (TEM) characterizes.Wherein, Fig. 2 a is the TEM photo of single target product, and from it, spherical target product is solid construction; Fig. 2 b is the high resolving power TEM photo of the nanometer sheet of target product shown in Fig. 2 a, and the high resolving power TEM photo of this single nanometer sheet has demonstrated nanometer sheet surface carbon striped clearly.
Fig. 3 is that target product to making uses one of result that X-ray diffraction (XRD) instrument characterizes.Can be found out by XRD spectra, the spectrogram of target product is identical with the standard spectrogram JCPDS Number:36-1451 of zinc oxide six side's phase structures.
Fig. 4 is one of result respectively intermediate product obtaining and the target product use Raman spectrometer making being characterized.The spectral line that curve a in spectrogram is target product, the spectral line that curve b is intermediate product; Can be found out by spectrogram, intermediate product and target product are all at 1340cm
-1and 1580cm
-1near have amorphous peak and the greying peak of two carbon, illustrate and wherein contain amorphous carbon and graphited carbon.
Embodiment
First buy from market or make by ordinary method:
Two hydration zinc acetates; Urea; Two hydration Trisodium Citrates; Glucose; Water; Deionized water; Ethanol; As one or more the mixed gas in the nitrogen of rare gas element, argon gas, helium.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, it it is first 0.64: 0.56: 0.05 according to the weight ratio between two hydration zinc acetates, urea, two hydration Trisodium Citrates, glucose and water: the ratio of 1.2: 48, two hydration zinc acetates, urea, two hydration Trisodium Citrates and glucose are dissolved in the water, obtain mixed solution.Again mixed solution being placed in to air-tight state, is to react 4h at 120 DEG C in temperature, obtains reaction solution.
Step 2, first carries out solid-liquid separation, washing and dry processing successively to reaction solution; Wherein, solid-liquid separation is treated to centrifugation, and rotating speed when separation is 3000r/min, and carrying out washing treatment is for being used deionized water and ethanol to clean, and drying treatment, for to dry at 10 DEG C, obtains intermediate product.Again intermediate product is placed in to inert gas atmosphere, 2h anneals at 300 DEG C; Wherein, rare gas element is nitrogen, make and be similar to shown in Fig. 1 and Fig. 2, and micro-nano structure zinc oxide-carbon compound ball as shown in the curve in Fig. 3 and Fig. 4.
Embodiment 2
The concrete steps of preparation are:
Step 1, it it is first 0.65: 0.55: 0.055 according to the weight ratio between two hydration zinc acetates, urea, two hydration Trisodium Citrates, glucose and water: the ratio of 1.1: 49, two hydration zinc acetates, urea, two hydration Trisodium Citrates and glucose are dissolved in the water, obtain mixed solution.Again mixed solution being placed in to air-tight state, is to react 3.5h at 130 DEG C in temperature, obtains reaction solution.
Step 2, first carries out solid-liquid separation, washing and dry processing successively to reaction solution; Wherein, solid-liquid separation is treated to centrifugation, and rotating speed when separation is 3500r/min, and carrying out washing treatment is for being used deionized water and ethanol to clean, and drying treatment, for to dry at 20 DEG C, obtains intermediate product.Again intermediate product is placed in to inert gas atmosphere, 1.8h anneals at 330 DEG C; Wherein, rare gas element is nitrogen, make and be similar to shown in Fig. 1 and Fig. 2, and micro-nano structure zinc oxide-carbon compound ball as shown in the curve in Fig. 3 and Fig. 4.
Embodiment 3
The concrete steps of preparation are:
Step 1, it it is first 0.66: 0.54: 0.06 according to the weight ratio between two hydration zinc acetates, urea, two hydration Trisodium Citrates, glucose and water: the ratio of 1: 50, two hydration zinc acetates, urea, two hydration Trisodium Citrates and glucose are dissolved in the water, obtain mixed solution.Again mixed solution being placed in to air-tight state, is to react 3h at 140 DEG C in temperature, obtains reaction solution.
Step 2, first carries out solid-liquid separation, washing and dry processing successively to reaction solution; Wherein, solid-liquid separation is treated to centrifugation, and rotating speed when separation is 4000r/min, and carrying out washing treatment is for being used deionized water and ethanol to clean, and drying treatment, for to dry at 30 DEG C, obtains intermediate product.Again intermediate product is placed in to inert gas atmosphere, 1.5h anneals at 350 DEG C; Wherein, rare gas element is nitrogen, make as depicted in figs. 1 and 2, and micro-nano structure zinc oxide-carbon compound ball as shown in the curve in Fig. 3 and Fig. 4.
Embodiment 4
The concrete steps of preparation are:
Step 1, it it is first 0.67: 0.53: 0.065 according to the weight ratio between two hydration zinc acetates, urea, two hydration Trisodium Citrates, glucose and water: the ratio of 0.9: 51, two hydration zinc acetates, urea, two hydration Trisodium Citrates and glucose are dissolved in the water, obtain mixed solution.Again mixed solution being placed in to air-tight state, is to react 2.5h at 150 DEG C in temperature, obtains reaction solution.
Step 2, first carries out solid-liquid separation, washing and dry processing successively to reaction solution; Wherein, solid-liquid separation is treated to centrifugation, and rotating speed when separation is 4500r/min, and carrying out washing treatment is for being used deionized water and ethanol to clean, and drying treatment, for to dry at 40 DEG C, obtains intermediate product.Again intermediate product is placed in to inert gas atmosphere, 1.3h anneals at 380 DEG C; Wherein, rare gas element is nitrogen, make and be similar to shown in Fig. 1 and Fig. 2, and micro-nano structure zinc oxide-carbon compound ball as shown in the curve in Fig. 3 and Fig. 4.
Embodiment 5
The concrete steps of preparation are:
Step 1, it it is first 0.68: 0.52: 0.07 according to the weight ratio between two hydration zinc acetates, urea, two hydration Trisodium Citrates, glucose and water: the ratio of 0.8: 52, two hydration zinc acetates, urea, two hydration Trisodium Citrates and glucose are dissolved in the water, obtain mixed solution.Again mixed solution being placed in to air-tight state, is to react 2h at 160 DEG C in temperature, obtains reaction solution.
Step 2, first carries out solid-liquid separation, washing and dry processing successively to reaction solution; Wherein, solid-liquid separation is treated to centrifugation, and rotating speed when separation is 5000r/min, and carrying out washing treatment is for being used deionized water and ethanol to clean, and drying treatment, for to dry at 50 DEG C, obtains intermediate product.Again intermediate product is placed in to inert gas atmosphere, 1h anneals at 400 DEG C; Wherein, rare gas element is nitrogen, make and be similar to shown in Fig. 1 and Fig. 2, and micro-nano structure zinc oxide-carbon compound ball as shown in the curve in Fig. 3 and Fig. 4.
Select respectively again as one or more the mixed gas in the nitrogen of rare gas element, argon gas, helium, repeat above-described embodiment 1~5, make equally as or be similar to as shown in Fig. 1 and Fig. 2, and micro-nano structure zinc oxide-carbon compound ball as shown in the curve in Fig. 3 and Fig. 4.
Obviously, those skilled in the art can carry out various changes and modification and not depart from the spirit and scope of the present invention micro-nano structure zinc oxide-carbon compound ball of the present invention and preparation method thereof.Like this, if to these amendments of the present invention with within modification belongs to the scope of the claims in the present invention and equivalent technologies thereof, the present invention is also intended to comprise these changes and modification interior.