CN101941677B - Method for preparing manganese oxide surface modified zinc oxide nano rod - Google Patents
Method for preparing manganese oxide surface modified zinc oxide nano rod Download PDFInfo
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- CN101941677B CN101941677B CN 201010269017 CN201010269017A CN101941677B CN 101941677 B CN101941677 B CN 101941677B CN 201010269017 CN201010269017 CN 201010269017 CN 201010269017 A CN201010269017 A CN 201010269017A CN 101941677 B CN101941677 B CN 101941677B
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Abstract
The invention discloses a method for preparing a manganese oxide surface modified zinc oxide nano rod and belongs to the technical field of inorganic functional materials. The method comprises the following steps of: carrying out complex reaction of sodium hydroxide and mixed aqueous solution of zinc acetate and manganese acetate so as to generate complex sol of zinc hydroxide and manganese hydroxide; and transferring the complex sol system into a hydrothermal kettle for contributing to hydrothermal reaction so as to directly prepare a zinc oxide nano rod and form manganese oxide nanoparticles on the surface of the zinc oxide nano rod simultaneously. The method has the advantages of simple preparation process, easy operation, suitability for large-scale preparation; and the prepared manganese oxide nanoparticle surface modified zinc oxide nano rod has the advantages of hexagonal sphalerite structure, smaller diameter of the manganese oxide nanoparticles on the surface, uniform particle distribution on the surface and large specific surface area, and can be used for preparing gas sensors, photocatalysts, photoelectric materials, catalyst carriers and the like.
Description
Technical field
The invention belongs to the inorganic functional material technical field, relate to a kind of preparation method of zinc-oxide nano bar.
Background technology
Nano zinc oxide material has good application prospect in sensor, electrooptical device, solar cell, secondary lithium battery negative material and photochemical catalyst, catalyst carrier; Particularly as semiconductive luminescent materials, in vacuum fluorescent display device, electroluminescent and field emission apparatus, be with a wide range of applications.
ZnO is a kind of semiconductor material with wide forbidden band, in order to realize that ZnO nano material is in the application of different field, usually utilize the metal ion mixing technology, in ZnO, add the energy gap that the metal ions such as Fe, Cu, Co, Cr, Mn or Mg are regulated ZnO, improve its luminescent properties and using value.
For metal ion-modified ZnO nano material, generally adopt gas-liquid-solid method (VLS) or chemical vapour deposition technique (CVD) preparation of condition harshness, complicated operation.The metal ion-modified ZnO nano material of general preparation, metal ion mixing is among ZnO body phase, but in order to realize that the good homogeneous of metal ion in ZnO distributes, said method needs preparation process or the expensive equipment of relatively high temperature, complexity, a large amount of comparision of production difficulties.
Summary of the invention
The invention provides a kind of zinc oxide nano rod material preparation method of utilizing manganese oxide to carry out surface modification.The method employing hydro-thermal reaction directly prepares the zinc-oxide nano bar material of surface modification, and is simple to operate, with low cost, is suitable for large-scale production.The zinc-oxide nano bar of prepared surface modification, zinc oxide are the nano bar-shape structure, and diameter is 200～400nm, and length is 2～3 μ m, and manganese oxide nano granule is evenly distributed on the zinc oxide nano rod surface, and its diameter is at 5～10nm, and specific area is large.This material non-toxic, physicochemical properties are stable, can be used for the fields such as gas sensor, photochemical catalyst, photoelectric device and catalyst carrier.
The present invention take acetate dihydrate manganese as the manganese source, adopts the hydro-thermal method process directly to prepare the zinc-oxide nano bar of manganese oxide surface modification take zinc acetate dihydrate as the zinc source.
Detailed technology scheme of the present invention is as follows:
A kind of preparation method of zinc-oxide nano bar of manganese oxide surface modification as shown in Figure 1, may further comprise the steps:
Step 1: with zinc acetate dihydrate ((Zn (Ac)
22H
2And acetate dihydrate manganese (Mn (Ac) O))
22H
2O) be solute, deionized water is solvent, and compound concentration is the zinc acetate of 0.05～1M and the mixed aqueous solution of manganese acetate, the mole that wherein adds acetate dihydrate manganese be equivalent to add 1.0～25.0% of zinc acetate dihydrate mole; Then add the urea of consistent dose to the mixed aqueous solution of zinc acetate and manganese acetate, then the limit slowly adds ethanol, and stir on the limit, until urea dissolves fully, obtains settled solution A.
Step 2: in step 1 gained settled solution A, add NaOH regulation system pH value to 12～14, obtain brown sol system B.
Step 3: the brown sol system B of step 2 gained is transferred in the teflon-lined water heating kettle, then 120～200 ℃ of Water Under thermal response degree 6～20 hours, obtain brown precipitation C.
Step 4: with drying, grind under step 3 gained brown precipitation C filtration, deionized water washing, 105～130 ℃ of conditions, namely get the zinc-oxide nano bar of manganese oxide surface modification.
Principle of the present invention is at first to utilize the complex reaction of NaOH and zinc acetate and manganese acetate mixed aqueous solution, generates the complex sol of zinc hydroxide and manganous hydroxide; Then the complex sol system is changed in the water heating kettle, form manganese oxide nano granule on its surface when being beneficial to hydro-thermal reaction and directly preparing the zinc-oxide nano bar.Wherein, urea plays the effect of stabilizing agent, main purpose is the reaction speed of control zinc acetate and NaOH, prevents that reaction speed very fast because of the reaction speed of zinc acetate under the aqueous solution and NaOH but manganese acetate and NaOH from can not get stable complex sol system slowly; In the hydrothermal reaction process under 120～200 ℃ of conditions, the decomposition rate of zinc hydroxide is very fast, generate rapidly Zinc oxide particles, and the decomposition rate of manganous hydroxide is slower, and the manganese oxide of generation can only be attached to zinc oxide surface, can't enter zincite crystal inside; Adopt hydro-thermal reaction directly to carry out the while crystallization to zinc oxide nano rod and manganese oxide nano granule, avoided the decline phenomenon of the excessive and specific area of hard aggregation, the crystal particle diameter of the nano particle that the high temperature crystallization causes.
The present invention compared with prior art has following advantage:
1, preparation process of the present invention is simple, and is easy to operate, is fit to extensive preparation.
2, the present invention prepares the zinc-oxide nano bar of manganese oxide nano granule surface modification, the X-ray diffraction analysis proof has six side's zincblende lattce structures (as shown in Figure 2), surface oxidation manganese particle diameter is less, in 5～10nm scope (as shown in Figure 3 and Figure 4), and particle distributes at surface uniform, and specific area is large.
3, the zinc-oxide nano bar range of application of the manganese oxide nano granule surface modification of the present invention's preparation is wider, can be used for preparing gas sensor, photochemical catalyst, photoelectric material and catalyst carrier etc.
Description of drawings
Fig. 1 is the process chart that the present invention prepares the zinc-oxide nano bar of manganese oxide nano granule surface modification.
Fig. 2 be the zinc-oxide nano bar of the manganese oxide nano granule surface modification for preparing of the present invention XRD figure (wherein the Mn molar content be the Zn mole 10%).
Fig. 3 be the zinc-oxide nano bar of the manganese oxide nano granule surface modification for preparing of the present invention scanning electron microscope (SEM) photograph (wherein the Mn molar content be the Zn mole 10%).
Fig. 4 for the height explanation transmission electron microscope photo of the zinc-oxide nano bar of the manganese oxide nano granule surface modification of this preparation (wherein the Mn molar content be the Zn mole 10%).
The specific embodiment
Embodiment one
At first compound concentration is the zinc acetate of 0.5～1M and the mixed aqueous solution of manganese acetate, the mole that wherein adds acetate dihydrate manganese be equivalent to add 10% of zinc acetate dihydrate mole; Then add the urea of consistent dose to the mixed aqueous solution of zinc acetate and manganese acetate, then the limit slowly adds ethanol, and the limit magnetic agitation until urea dissolves fully, obtains settled solution A; Then in settled solution A, add NaOH regulation system pH value to 14, obtain brown sol system B; Again brown sol system B is transferred in the teflon-lined water heating kettle, 160 ℃ of Water Under thermal response degree 8 hours, obtain brown precipitation C; With drying, grind under brown precipitation C filtration, deionized water washing, 110 ℃ of conditions, namely get the zinc-oxide nano bar of manganese oxide surface modification at last.The observed under electron microscope manganese oxide nano granule covers the zinc oxide nano rod surface.The manganese oxide average diameter is 8nm, the particle ball-type, evenly.Zinc oxide is bar-shaped, and zinc oxide is the nano bar-shape structure, and average diameter is 300nm, and length is 2.5 μ m; The XRD measurement result shows that tin ash is six side's zincblende lattce structures; The BET specific area is 65.8m
2/ g.
Embodiment two
At first compound concentration is the zinc acetate of 0.5～1M and the mixed aqueous solution of manganese acetate, the mole that wherein adds acetate dihydrate manganese be equivalent to add 5% of zinc acetate dihydrate mole; Then add the urea of consistent dose to the mixed aqueous solution of zinc acetate and manganese acetate, then the limit slowly adds ethanol, and the limit magnetic agitation until urea dissolves fully, obtains settled solution A; Then in settled solution A, add NaOH regulation system pH value to 12, obtain brown sol system B; Again brown sol system B is transferred in the teflon-lined water heating kettle, 120 ℃ of Water Under thermal response degree 20 hours, obtain brown precipitation C; With drying, grind under brown precipitation C filtration, deionized water washing, 120 ℃ of conditions, namely get the zinc-oxide nano bar of manganese oxide surface modification at last.The observed under electron microscope manganese oxide nano granule covers the zinc oxide nano rod surface.The manganese oxide average diameter is 9nm, the particle ball-type, evenly.Zinc oxide is bar-shaped, and zinc oxide is the nano bar-shape structure, and average diameter is 300nm, and length is 3 μ m; The XRD measurement result shows that tin ash is six side's zincblende lattce structures; The BET specific area is 35.6m
2/ g.
Embodiment three
At first compound concentration is the zinc acetate of 0.5～1M and the mixed aqueous solution of manganese acetate, the mole that wherein adds acetate dihydrate manganese be equivalent to add 20% of zinc acetate dihydrate mole; Then add the urea of consistent dose to the mixed aqueous solution of zinc acetate and manganese acetate, then the limit slowly adds ethanol, and the limit magnetic agitation until urea dissolves fully, obtains settled solution A; Then in settled solution A, add NaOH regulation system pH value to 14, obtain brown sol system B; Again brown sol system B is transferred in the teflon-lined water heating kettle, 120 ℃ of Water Under thermal response degree 20 hours, obtain brown precipitation C; With drying, grind under brown precipitation C filtration, deionized water washing, 120 ℃ of conditions, namely get the zinc-oxide nano bar of manganese oxide surface modification at last.The observed under electron microscope manganese oxide nano granule covers the zinc oxide nano rod surface.The manganese oxide average diameter is 10nm, the particle ball-type, evenly.Zinc oxide is bar-shaped, and zinc oxide is the nano bar-shape structure, and average diameter is 200nm, and length is 2.5 μ m; The XRD measurement result shows that tin ash is six side's zincblende lattce structures; The BET specific area is 85.9m
2/ g.
Claims (1)
1. the preparation method of the zinc-oxide nano bar of a manganese oxide surface modification may further comprise the steps:
Step 1: take zinc acetate dihydrate and acetate dihydrate manganese as solute, deionized water is solvent, compound concentration is the zinc acetate of 0.05～1M and the mixed aqueous solution of manganese acetate, the mole that wherein adds acetate dihydrate manganese be equivalent to add 1.0～25.0% of zinc acetate dihydrate mole; Then add the urea of consistent dose to the mixed aqueous solution of zinc acetate and manganese acetate, then the limit slowly adds ethanol, and stir on the limit, until urea dissolves fully, obtains settled solution A;
Step 2: in step 1 gained settled solution A, add NaOH regulation system pH value to 12～14, obtain brown sol system B;
Step 3: the brown sol system B of step 2 gained is transferred in the teflon-lined water heating kettle, then 120～200 ℃ of Water Under thermal responses 6～20 hours, obtain brown precipitation C;
Step 4: with drying, grind under step 3 gained brown precipitation C filtration, deionized water washing, 105～130 ℃ of conditions, namely get the zinc-oxide nano bar of manganese oxide surface modification.
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| CN102251285B (en) * | 2011-07-18 | 2013-06-05 | 北京工业大学 | Soakage controllable zinc oxide single crystal surface modification method |
| CN102701335B (en) * | 2012-06-19 | 2014-04-02 | 深圳市华水环保科技有限公司 | Ion electrode, preparation method of ion electrode, high-voltage pulse three-dimensional electrode reactor |
| CN105336500B (en) * | 2015-10-16 | 2016-10-05 | 景德镇陶瓷大学 | A kind of in-situ modified processing method of ZnO nanorod thin film and the modified film of acquisition thereof |
| CN105289582B (en) * | 2015-10-30 | 2017-11-10 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of zinc oxide nano rod supports the preparation method of oxidation manganese-based catalyst |
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