CN102774874B - Novel preparation method of nano-zinc oxide - Google Patents
Novel preparation method of nano-zinc oxide Download PDFInfo
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- CN102774874B CN102774874B CN201210192184.7A CN201210192184A CN102774874B CN 102774874 B CN102774874 B CN 102774874B CN 201210192184 A CN201210192184 A CN 201210192184A CN 102774874 B CN102774874 B CN 102774874B
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Abstract
The invention discloses a novel preparation method of nano-zinc oxide, belonging to the technical field of the perpetration of a semiconductor and an optical material. The method comprises the following steps of: firstly, preparing nano-net structure zinc oxide, and generating nano-zinc oxide in the high-water absorbability resin due to the guide functions of a high-water absorbability resin which is taken as a template and the nano-net structure. The preparation method controls the size and the morphology of the prepared nano-structure zinc oxide due to the characteristic of the three-dimensional net structure and the slow release, so that the prepared zinc oxide product reaches to the nano-order, is relatively even in granularity, and has the unique nano-net structure. The polygonal zinc oxide with the unique morphology can be further prepared; and the novel preparation method further has the advantages that the technological conditions are easily controlled and the cost is relatively low.
Description
Technical field
The invention belongs to semi-conductor and optical material preparing technical field, particularly a kind of preparation method of novel nano zinc oxide.
Background technology:
The semi-conductive energy gap of ZnO is 3.37eV, and laser beam can reach 60eV, has excellent piezoelectricity and photoelectric properties.The research that ZnO semi-conductor is used as third generation semi-conductor and optics material of new generation has in recent years caused people's extensive concern, nano zine oxide is as the perfect adaptation of nano material and important conductor oxidate, and the granular of particle and specific surface area sharply increase and make nano-ZnO have the not available new character of its bulk material.Therefore, nano-ZnO has specific function that general ZnO material cannot be equal to and new purposes in magnetic, the field such as optical, electrical.It is that novel material ，Ye Shi China " 863 " that 21 century countries in the world throwing huge fund develops plans the key subjects of tackling key problems.At present, the annual requirement of all kinds of zinc oxide of China is 1,500,000 tons of left and right, and demand improves constantly, and ZnO must have more wide market outlook from now on.Therefore, the technology of preparing of nano zine oxide and the exploitation of method seem particularly important.
Current, the method of preparing nano zine oxide mainly comprises: chemical deposition method, sol-gel method, microemulsion method, spray pyrolysis, hydrothermal synthesis method, solid reaction process, induced with laser chemical method etc., the structure of the nano zine oxide that diverse ways makes and size and uniformity coefficient thereof have larger difference.And the pattern of nano zine oxide and size and uniformity coefficient thereof directly affect the performance of product.The performances such as optical, electrical, the magnetic of the zinc oxide of different structure, different size have very large difference.
A large amount of researchs show, the principal element that affects nano zine oxide microtexture and performance is speed of reaction and structure-directing effect.Speed of reaction is too high, can make product unite, and finally loses nanostructure; The Effects on Microstructure of structure directing agent microtexture and the pattern of product.
High hydrophilous resin is a kind of functional high molecule material with unique water-absorbing-retaining ability, it is to consist of lightly crosslinked macromolecular chain, water insoluble and organic solvent, can absorb the water of own wt hundred times and even thousands of times and be gel, and this gel water retention capacity is strong and nonpoisonous and tasteless.The microtexture of this gel is studied to discovery, the water that sucks High hydrophilous resin inside has three kinds of states, be respectively free water (Free water), intermediate state water (Intermediate water) and in conjunction with water (Bound water), the overwhelming majority is free water.Wherein in conjunction with the functional group on water and macromolecular chain, there is strong hydrogen bond action, this part water no longer has the properties of common moisture, for example its zero pour is lower than 0 ℃, in some High hydrophilous resin, can reach-100 ℃, free water interacts with these functional groups hardly, its zero pour or 0 ℃, be called again and freeze water; Intermediate state water with fall between, and in conjunction with there being certain hydrogen bond action between water, its zero pour is below 0 ℃, in conjunction with water zero pour.Macromolecular chain, intermediate state water and a large amount of free water being strapped in by hydrogen bond action in conjunction with water in the three-dimensional network of macromolecular chain (structural models as shown in Figure 1), and then form cellular texture connected with each other one by one, even if so pressurization can not extruded water yet to hydrogel, thereby make High hydrophilous resin there is excellent water-absorbing-retaining function.
High hydrophilous resin after water suction has the character feature of the gentle On The Drug Release of three-dimensional macromolecule network structure opening, these features can be used for designing novel nano-material theoretically: the feature slowly discharging can be controlled speed of response, and the three-dimensional macromolecule network opening can be used as microtexture and the pattern that soft template and directed agents are adjusted product.
Summary of the invention:
The preparation method who the object of this invention is to provide a kind of novel nano zinc oxide, is characterized in that, employing High hydrophilous resin is template, utilizes its template and structure-directing effect at the inner nano zine oxide that generates of High hydrophilous resin, and concrete preparation process is as follows:
(1) preparation of Nanostructure Network zinc oxide
A: preparation ammonia soln and zinc solution, the volumetric concentration of ammonia solution is 5%-15%, the concentration of zinc solution is 0.75～2g/L;
B: prepare ammoniacal liquor gel smalls: the High hydrophilous resin of getting certain mass joins in the ammonia soln of preparation, place 12～24h and reach adsorption equilibrium to system, now system is gelatinous amine lyogel, the sieve top sieve that is 0.5-1.5 micron in aperture by this solidifying amine lyogel becomes smalls, and sieve several times more, to guarantee its gel smalls uniform particles, avoid producing strip gel when once sieving the contact area between reactant is reduced, thereby it is insufficient to cause reaction to be carried out;
C: the gel smalls in step B and zinc solution are added in reactor simultaneously, stir it is fully mixed, react 2～3h in 45～55 ℃ of waters bath with thermostatic control;
D: centrifugal under the rotating speed of 5000～10000rpm after the resulting reaction solution of step C is standing, centrifugation time is 5～10min;
E: add a large amount of dehydrated alcohols in the product after centrifugal and stir for some time, by the precipitation standing separation of gained, by washing of precipitate, be drying to obtain zinc oxide/resin composite body
;three-dimensional netted nano material is scattered here and there in gained clear liquid;
(2) take Nanostructure Network prepares polygonal nanometer zinc oxide as template
A: add certain mass ammoniacal liquor to be made into the ammonia soln that volumetric concentration is 5%-15% in the clear liquid that contains Nanostructure Network of step () E gained;
B: add again the solid zinc salt of certain mass in the solution of step (two) A, and make its concentration identical with the zinc solution concentration of step () A;
C: the reaction solution of step (two) B is added in reactor, stir it is fully mixed, react 2～3h in 45～55 ℃ of waters bath with thermostatic control;
D: gained precipitated product is leached, washing, dry;
E: the air atmosphere roasting 4-5h by step (two) D products therefrom at 400～600 ℃, obtains having the nano zine oxide of cerioid structure.
Described zinc solution is the aqueous solution of zinc nitrate, zinc chloride or zinc sulfate.
Described High hydrophilous resin is that natural polymer subsystem High hydrophilous resin, employing vinylformic acid or the propionic acid amide that raw material prepares is that synthetic that raw material prepares is High hydrophilous resin for adopting starch or Mierocrystalline cellulose.
The invention has the beneficial effects as follows in preparation method, employing High hydrophilous resin is template, utilize the feature of the gentle On The Drug Release of its tridimensional network to control size and the pattern of prepared nanostructured zinc oxide, make prepared oxidized zinc products reach nanometer scale, granularity is comparatively even, and has unique Nanostructure Network.Then take this reticulated structure again as template, prepared the cerioid zinc oxide with unique morphology; In addition, method of the present invention also has advantages of the easy to control and lower cost of processing condition.
Accompanying drawing explanation
Fig. 1 (a, b, c, d) is transmission electron microscope (TEM) figure of several reticulated structure zinc oxide.
Fig. 2 (a, b, c, d) is scanning electron microscope (SEM) figure of several cerioid zinc oxide.
Embodiment
The invention provides a kind of preparation method of novel nano zinc oxide.Below in conjunction with accompanying drawing, be further described.First the present invention prepares size and the pattern that feature that Nanostructure Network zinc oxide utilizes the gentle On The Drug Release of tridimensional network has been controlled prepared nanostructured zinc oxide in preparation method, make prepared oxidized zinc products reach nanometer scale, granularity is comparatively even, and there is unique Nanostructure Network, as shown in transmission electron microscope (TEM) figure of several reticulated structure zinc oxide of Fig. 1 (a, b, c, d).Then utilize the guide effect of its template and Nanostructure Network at the inner cerioid zinc oxide with unique morphology that generates of High hydrophilous resin, as shown in scanning electron microscope (SEM) figure of several cerioid zinc oxide of Fig. 2 (a, b, c, d).
The reaction principle of preparing nano zine oxide is:
(CH
2)
6n
4(resin gel smalls)+6H
2o → 6HCHO+4NH
3
NH
3?+?H
2O?→?NH
4 ++OH
-
Zn
2+?+?2OH
-?→?ZnO?+?H
2O
Utilize the coprecipitation reaction of zinc salt and vulkacit H solution to generate zinc oxide/resin composite body, then make polygonal nanometer zinc oxide through high-temperature roasting, exemplify embodiment as follows.
Steps A: the zinc nitrate solution that the ammonia soln that preparation 100ml volumetric concentration is 10% and 100ml concentration are 1.0g/L;
Step B: bulk employing starch or the Mierocrystalline cellulose of getting 0.5g are that the natural polymer subsystem High hydrophilous resin that raw material prepares joins in the ammonia soln of preparation, placing 22h adsorbs and reaches balance to system, now system is gel, is that the sieve top sieve of 1 micron of left and right becomes smalls (sieving 2-4 time) by this gel in aperture;
Step C: the gel smalls in step B and zinc nitrate solution are added respectively in reactor, stir it is fully mixed, react 2.5h in 88 ℃ of waters bath with thermostatic control;
Step D: centrifugal under the rotating speed of 5000～10000rpm after the resulting reaction solution of step C is standing, centrifugation time is 8-10min;
Step e: add a large amount of dehydrated alcohols in the product after centrifugal and stir for some time, by the static separation of the precipitated product of gained, by washing of precipitate, be drying to obtain zinc oxide/resin composite body; A large amount of three-dimensional netted nano materials are dispersed in clear liquid.
Step F: add the ammoniacal liquor wiring solution-forming of certain mass in the filtrate of containing Nanostructure Network of step e gained in embodiment 1, and to make its volumetric concentration be 12%;
Step G: add again the solid nitric acid zinc of certain mass in the solution of steps A, and to make its concentration be 1.0g/L;
Step H: the reaction solution in step B is added in reactor, stir it is fully mixed, react 2.5h in 88 ℃ of waters bath with thermostatic control;
Step I: gained precipitated product is leached, washing, dry;
Step J: step D products therefrom, at roasting 4-5h at 500 ℃, is obtained having the nano zine oxide of the 5-50nm of cerioid structure.
embodiment 2
Steps A: accurately prepare the ammonia soln that 50ml volumetric concentration is 5-15%.
Step B: adding the microspheric employing vinylformic acid of 0.1g or propionic acid amide in the solution of steps A is that synthetic that raw material prepares is High hydrophilous resin, 24h is to balance in absorption.
Step C: accurately prepare the solder(ing)acid that 50ml concentration is 0.8g/L, and joined in the gelling system in step B, fully mix, water bath with thermostatic control heating 3h at 45-55 ℃.
Step D: centrifugal under the rotating speed of 5000～10000rpm after the resulting reaction solution of step C is standing, centrifugation time is 8-10min;
Step e: add a large amount of dehydrated alcohols in the product after centrifugal and stir for some time, by the static separation of the precipitated product of gained, by washing of precipitate, be drying to obtain zinc oxide/resin composite body; A large amount of three-dimensional netted nano materials are dispersed in clear liquid.
Step F: add the ammoniacal liquor wiring solution-forming of certain mass in the filtrate of containing Nanostructure Network of step e gained in embodiment 1, and to make its volumetric concentration be 9%;
Step G: add again the solid nitric acid zinc of certain mass in the solution of steps A, and to make its concentration be 0.8g/L;
Step H: the reaction solution in step B is added in reactor, stir it is fully mixed, react 3h in 45-55 ℃ of water bath with thermostatic control;
Step I: gained precipitated product is leached, washing, dry;
Step J: step D products therefrom, at roasting 4-5h at 450 ℃, is obtained having the nano zine oxide of the 5-50nm of cerioid structure.
embodiment 3
Steps A: accurately prepare the ammonia soln that 50ml concentration is 5%-15%.
Step B: add the microspheroidal High hydrophilous resin of the 0.2g of embodiment 1 in the solution of steps A, 24h is to balance in absorption.
Step C: accurately prepare the zinc sulfate solution that 50ml concentration is 1.8g/L, and joined in the gelling system in step B, fully mix, water bath with thermostatic control heating 2-3h at 45-55 ℃.
Step D: centrifugal under the rotating speed of 5000～10000rpm after the resulting reaction solution of step C is standing, centrifugation time is 8-10min;
Step e: add a large amount of dehydrated alcohols in the product after centrifugal and stir for some time, by the static separation of the precipitated product of gained, by washing of precipitate, be drying to obtain zinc oxide/resin composite body; A large amount of three-dimensional netted nano materials are dispersed in clear liquid.
Step F: add the ammoniacal liquor wiring solution-forming of certain mass in the filtrate of containing Nanostructure Network of step e gained in embodiment 1, and to make its concentration be 6%;
Step G: add again the solid nitric acid zinc of certain mass in the solution of steps A, and to make its concentration be 1.8g/L;
Step H: the reaction solution in step B is added in reactor, stir it is fully mixed, react 3h in 50 ℃ of waters bath with thermostatic control;
Step I: gained precipitated product is leached, washing, dry;
Step J: step D products therefrom, at roasting 4-5h at 550 ℃, is obtained having the nano zine oxide of cerioid structure.
Claims (3)
1. a preparation method for nano zine oxide, is characterized in that, employing High hydrophilous resin is template, utilizes its template and structure-directing effect at the inner nano zine oxide that generates of High hydrophilous resin, and concrete preparation process is as follows:
(1) preparation of Nanostructure Network zinc oxide
A: preparation ammonia soln and zinc solution, the volumetric concentration of ammonia soln is 5%-15%, the concentration of zinc solution is 0.75～2g/L;
B: preparation feedback gel smalls: the High hydrophilous resin of getting certain mass joins in the ammonia soln of preparation, place 12～24h and reach adsorption equilibrium to system, now system is gel, the sieve top sieve that by this gel in aperture is 1-2 micron becomes smalls, by gel twice of sieve top sieve, to guarantee its gel smalls uniform particles, avoid producing strip gel when once sieving the contact area between reactant is reduced, thereby it is insufficient to cause reaction to be carried out;
C: the gel smalls in step B and zinc solution are added in reactor simultaneously, stir it is fully mixed, react 2～3h in 45～55 ℃ of waters bath with thermostatic control;
D: centrifugal under the rotating speed of 5000～10000rpm after the resulting reaction solution of step C is standing, centrifugation time is 5～10min;
E: add a large amount of dehydrated alcohols in the product after centrifugal and stir for some time, by the precipitation standing separation of gained, by washing of precipitate, be drying to obtain zinc oxide/resin composite body
;the three-dimensional netted nano material that is scattered here and there in gained clear liquid,
(2) take Nanostructure Network prepares polygonal nanometer zinc oxide as template
A: add the ammoniacal liquor wiring solution-forming of certain mass in the clear liquid that contains Nanostructure Network of step () E gained, and make its concentration identical with the ammonia soln concentration of step () A;
B: add again the solid zinc salt of certain mass in the solution of step (two) A, and make its concentration identical with the zinc solution concentration of step () A;
C: the reaction solution of step (two) B is added in reactor, stir it is fully mixed, react 2～3h in 45～55 ℃ of waters bath with thermostatic control;
D: gained precipitated product is leached, washing, dry;
E: the air atmosphere roasting 4-5h by step (two) D products therefrom at 400～600 ℃, obtains having the nano zine oxide of cerioid structure.
2. a kind of preparation method of nano zine oxide according to claim 1, is characterized in that, described zinc solution is the aqueous solution of zinc nitrate, zinc chloride or zinc sulfate.
3. a kind of preparation method of nano zine oxide according to claim 1, it is characterized in that, described High hydrophilous resin is that the natural polymer subsystem High hydrophilous resin that raw material prepares is that synthetic that raw material prepares is High hydrophilous resin with adopting vinylformic acid or propionic acid amide for adopting starch or Mierocrystalline cellulose.
?
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| CN110436511B (en) * | 2019-09-10 | 2021-12-10 | 安徽锦华氧化锌有限公司 | Preparation method of nano zinc oxide with net structure |
| CN113277546B (en) * | 2021-04-15 | 2022-05-20 | 蚌埠学院 | Preparation method of gold nanoparticle implanted three-dimensional zinc oxide nano network material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1727283A (en) * | 2005-07-25 | 2006-02-01 | 大连交通大学 | Method for preparing superfine zinc oxide and crystal whisker of zinc oxide |
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| CN1727283A (en) * | 2005-07-25 | 2006-02-01 | 大连交通大学 | Method for preparing superfine zinc oxide and crystal whisker of zinc oxide |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2003-286028A 2003.10.07 |
| 李彦生等.离子交换法制备纳米ZnO及其光催化性能.《大连交通大学学报》.2008,第29卷(第3期),61-63. |
| 离子交换法制备纳米ZnO及其光催化性能;李彦生等;《大连交通大学学报》;20080630;第29卷(第3期);61-63 * |
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