CN103011256B - Method for preparing zinc oxide nanorod arrays in extra-large area - Google Patents
Method for preparing zinc oxide nanorod arrays in extra-large area Download PDFInfo
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- CN103011256B CN103011256B CN201210587236.0A CN201210587236A CN103011256B CN 103011256 B CN103011256 B CN 103011256B CN 201210587236 A CN201210587236 A CN 201210587236A CN 103011256 B CN103011256 B CN 103011256B
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Abstract
The invention discloses a method for preparing zinc oxide nanorod arrays in an extra-large area. The preparation method comprises the following steps of: preprocessing a zinc sheet and taking the preprocessed zinc sheet as a growth substrate for later use; putting the growth substrate into a precursor containing a water-soluble labile zinc-ammonia complex, and putting the substrate into a high-pressure reactor to grow and react for 8-24h in a sealing manner at the temperature of 92-94 DEG C; and taking the reacted growth substrate out, and washing and drying the reacted growth substrate, wherein grey white matters growing on the surface of the growth substrate are zinc oxide nanorod arrays. The zinc oxide nanorods prepared by using the method nearly completely cover each surface of the substrate, and the zinc sheet as the growth substrate can be very large; and the method disclosed by the invention is simple in synthesis steps, good in repeatability, high in product quality, fewer in defects, suitable for being applied to devices, such as dye-sensitized solar cells and lithium ion batteries and is particularly suitable for photocatalyst and industrial large-scale production.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, specifically a kind of overlarge area prepares the method for nanometic zinc oxide rod array.
Background technology
Zinc oxide is the direct wide bandgap semiconductor materials of a kind of II-VI group, and under room temperature, energy gap is 3.37eV, and exciton bind energy is up to 60meV, and therefore it is the important photoelectric material with near ultraviolet absorption and luminosity.Compared with block zinc oxide, one-dimensional zinc oxide nanometer material has the features such as unique small-size effect, quantum confined effect and high-specific surface area, makes it in photochemical catalysis, magnetic, light emission, sensitivity characteristic, electricity, photoconduction, electricity and calorifics etc., show unique performance.In recent years, along with the improvement of technology of preparing, going deep into and development of nano zinc oxide material research, the growth technique of Synthetic Routes of One-dimensional ZnO Nanorods array have also been obtained perfect, but a kind of with low cost, product high quality is proposed, green non-poisonous, big area, the method for preparing Synthetic Routes of One-dimensional ZnO Nanorods array reliably remain a challenge.The method of current synthesizing one-dimensional nanometic zinc oxide rod array mainly contains two kinds: vapor phase process and liquid phase method.Vapor phase process comprises chemical Vapor deposition process and physical vaporous deposition, and general preparation temperature is higher than 450 DEG C, and gained crystal mass is high, but apparatus expensive, cost are high, preparation temperature is high, is unfavorable for a large amount of synthesis, can not meet the requirement of big area industry preparation far away.By contrast, Liquid preparation methods temperature is low, equipment is simple, cost is low, is more conducive to synthesize to adapt to industrialization demand in a large number, but generally oxygen defect is many, and crystalline quality is not high enough.General liquid phase method comprises the precipitator method, hydrothermal method, sol-gel method, hydrolysis method etc., and wherein hydrothermal method is more conventional.Adopt hydrothermal method to prepare Synthetic Routes of One-dimensional ZnO Nanorods array and be mainly divided into two steps, the preparation of zinc oxide seed layer on the first step substrate, second step prepares reaction soln and substrate is placed in precursors grows array.The preparation of Seed Layer adds the triviality of experiment, and adopt single stage method directly to prepare step that nano-wire array can simplify experiment greatly.Yang Heqing etc. in " Crystal growth and design " the 8th volume the 3rd phase in 2008, article " the Large-scale growth of highly oriented ZnO nanorodarrays in the Zn-NN that 1039-1043 page is delivered
3h
2o hydrothermal system " in propose and use zinc metal sheet to do zinc source to be put in certain density ammonia soln directly in the method for zinc metal sheet previous step growing zinc oxide nanorod.But this method needs zinc metal sheet sanding and polishing, utilize zinc atom exposed on zinc metal sheet for zinc source growing nano linear array, through test of many times, find that this method repeatability is not strong, reliable not, products therefrom not necessarily covers zinc metal sheet comprehensively, and crystalline quality is not high, cannot meet the demand of suitability for industrialized production and application.The organism in the photocatalysis performance degradation liquid of nano zine oxide is utilized to be an important now application in addition, but the nano zinc oxide material used at present generally is Powdered, drop in solution the solution separating that is not easy and is degraded, if the nano zine oxide growth used just can realize on substrate simply with solution separating, therefore proposing a kind of method that big area simple and reliable on zinc metal sheet prepares high-quality zinc oxide nanometer stick array has important meaning for this area.
Summary of the invention
The object of the invention is to for above-mentioned the deficiencies in the prior art, provide a kind of overlarge area to prepare the method for nanometic zinc oxide rod array.The method is simple and reliable, can prepare high-quality nanometic zinc oxide rod array on the zinc metal sheet of arbitrary dimension and thickness.Being also advantageous in that of the method is green non-poisonous, pollution-free, and repeatability is strong, and reliability is strong, and reactions steps is simple, mild condition, big area can prepare, is conducive to industrialization scale operation.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of method that overlarge area prepares nanometic zinc oxide rod array, comprise the steps:
A, using stand-by as growth substrate after zinc metal sheet pre-treatment;
B, described growth substrate is put into the precursor liquid of the labile zinc ammonia complex of containing water-soluble, be placed in autoclave 92 ~ 94 DEG C of sealing growth responses 8 ~ 24 hours;
C, reacted growth substrate to be taken out, cleaning, dry, the canescence material of described growth substrate surface-borne, i.e. described nanometic zinc oxide rod array.
Preferably, in steps A, the thickness of described zinc metal sheet is 0.02 ~ 1mm.
Preferably, in steps A, described pre-treatment is: first described zinc metal sheet is carefully cleaned with liquid detergent, then uses acetone and deionized water ultrasonic cleaning respectively.
Preferably, in step B, described growth substrate vertically puts into or curlingly puts into the precursor liquid of the labile zinc ammonia complex of containing water-soluble.
Further preferably, the size of described growth substrate is not limit, changeable, and large extremely described autoclave can load.
Preferably, in step B, the precursor liquid of the labile zinc ammonia complex of described containing water-soluble is dissolved in deionized water by zinc nitrate hexahydrate or zinc acetate, adds that ammoniacal liquor mixes; The zinc nitrate hexahydrate added in often liter of deionized water or zinc acetate are 0.8 ~ 5mmol, and the ammoniacal liquor added is 50 ~ 125ml.
Further preferably, described mixing is specially: magnetic agitation 10 ~ 30min after supersound process 3 ~ 5min.
Preferably, in step B, the time of described sealing growth response is 10 ~ 24 hours.
Compared with prior art, the present invention has following beneficial effect:
1, this preparation method is mixed to form water miscible labile zinc ammonia complex by zinc salt and ammonia soln, serves as the growth cores of zinc oxide in reaction soln; At a certain temperature subsequently, growth cores is deposited on induced growth Synthetic Routes of One-dimensional ZnO Nanorods array on zinc metal sheet, the large-area nanometic zinc oxide rod array of final formation;
2, this preparation method can on the zinc metal sheet two sides of arbitrary dimension (determining according to container), and the nanometic zinc oxide rod array of controlled synthesis large-area high-quality is applied particularly photochemical catalysis for nano zinc oxide material and provided more wide prospect;
3, this preparation method can realize preparing nanometic zinc oxide rod array in a large number in flexible substrates (thinner zinc paper tinsel (about 0.02 ~ 0.05mm));
4, reactant wide material sources, with low cost, green non-pollution, conversion unit requires low, temperature of reaction low (lower than 100 DEG C), and technique is simple, and only a step completes, and is easy to industrialization scale operation.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the low power SEM figure that the surface of embodiment 1 covers with the zinc metal sheet of nanometic zinc oxide rod array;
Fig. 2 is the high power SEM figure that the surface of embodiment 1 covers with the zinc metal sheet of nanometic zinc oxide rod array;
Fig. 3 is the high-resolution-ration transmission electric-lens photo figure of the zinc oxide nano rod of embodiment 1; Wherein, a is pattern photo, and b is electron-diffraction diagram.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make certain adjustments and improvements.These all belong to protection scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.
embodiment 1
The method that zinc metal sheet is prepared overlarge area and high quality nanometic zinc oxide rod array of the present embodiment, concrete steps are as follows:
1, getting 0.1g zinc nitrate hexahydrate is dissolved in 200ml deionized water, add 10ml ammoniacal liquor supersound process and carry out magnetic agitation after 5 minutes 20 minutes until zinc nitrate hexahydrate and ammoniacal liquor fully dissolve mixing, form homogeneous, stable, colourless solution, the precursor liquid needed for hydro-thermal reaction.In this precursor liquid, zinc nitrate hexahydrate and ammoniacal liquor are mixed to form water miscible labile zinc ammonia complex, serve as the growth cores of zinc oxide in precursor liquid;
2, get the zinc metal sheet of traditional Chinese medicines purchase as growth substrate, thickness is about 0.15mm, and size is about 40cm × 10cm × 0.15mm; First carefully clean with liquid detergent, then use acetone and deionized water ultrasonic cleaning 10 minutes respectively, dry up with nitrogen, stand-by as growth substrate;
3, the growth substrate rolling into barrel-shape handled well in step 2 is put into the precursor liquid that step 1 prepares, be placed in autoclave and tighten sealing;
4, the reactor installed in step 3 is placed in baking oven and carries out growth response at 94 DEG C, the time is 12h; At this temperature, induced growth Synthetic Routes of One-dimensional ZnO Nanorods array on the zinc metal sheet that growth cores is deposited on lattice match, finally forms large-area nanometic zinc oxide rod array;
5, after reaction terminates, the growth substrate in step 4 is taken out; Repeatedly rinse 3 minutes with deionized water, wash surface impurity off, after cleaning, nitrogen dries up, and can see that on zinc metal sheet, two sides and side have all been covered with the linen material of one deck, this material is obtained nanometic zinc oxide rod array.
The low power of nanometic zinc oxide rod array prepared by the present embodiment and high power SEM figure are as depicted in figs. 1 and 2, can find out that from Fig. 1,2 (diameter is about 100nm to large-area nanometic zinc oxide rod array, length is about 10 μm) grow on zinc metal sheet uniformly, each face of almost 100% covering substrate.As shown in Figure 3, wherein a is pattern photo to the zinc oxide nano rod high-resolution-ration transmission electric-lens photo of the present embodiment, and b is for choosing electron-diffraction diagram.From Fig. 3 a, the diameter of single nanometer rod is about 100nm; Grown along [0001] direction by the zinc oxide nano rod of the known gained of Fig. 3 b, spacing of lattice is 0.52 dust.
embodiment 2
The method that zinc metal sheet is prepared overlarge area and high quality nanometic zinc oxide rod array of the present embodiment, concrete steps are as follows:
1, getting 0.05g (0.168mmol) zinc nitrate hexahydrate is dissolved in 200ml deionized water, add 25ml ammoniacal liquor supersound process and carry out magnetic agitation after 3 minutes 10 minutes until zinc nitrate hexahydrate and ammoniacal liquor fully dissolve mixing, form homogeneous, stable, colourless solution, the precursor liquid needed for hydro-thermal reaction.In this precursor liquid, zinc nitrate hexahydrate and ammoniacal liquor are mixed to form water miscible labile zinc ammonia complex, serve as the growth cores of zinc oxide in precursor liquid;
2, get zinc metal sheet that traditional Chinese medicines buy as growth substrate, thickness is about 0.02mm, first carefully cleans with liquid detergent, then uses acetone and deionized water ultrasonic cleaning 15 minutes respectively, dries up with nitrogen, stand-by as growth substrate; Zinc metal sheet size does not limit, changeable, can load to reaction vessel greatly;
3, the growth substrate handled well in step 2 is directly vertically put into the precursor liquid that step 1 prepares, be placed in autoclave and tighten sealing;
4, the reactor installed in step 3 is placed in baking oven and carries out growth response at 94 DEG C, the time is 8h; At this temperature, induced growth Synthetic Routes of One-dimensional ZnO Nanorods array on the zinc metal sheet that growth cores is deposited on lattice match, finally forms large-area nanometic zinc oxide rod array;
5, after reaction terminates, the growth substrate in step 4 is taken out; Repeatedly rinse 5 minutes with deionized water, wash surface impurity off, after cleaning, nitrogen dries up, and can see that on zinc metal sheet, two sides and side have all been covered with the linen material of one deck, this material is obtained nanometic zinc oxide rod array.
embodiment 3
The method that zinc metal sheet is prepared overlarge area and high quality nanometic zinc oxide rod array of the present embodiment, concrete steps are as follows:
1, getting 0.3g (1.008mmol) zinc nitrate hexahydrate is dissolved in 200ml deionized water, add 20ml ammoniacal liquor supersound process and carry out magnetic agitation after 3 minutes 30 minutes until zinc nitrate hexahydrate and ammoniacal liquor fully dissolve mixing, form homogeneous, stable, colourless solution, the precursor liquid needed for hydro-thermal reaction.In this precursor liquid, zinc nitrate hexahydrate and ammoniacal liquor are mixed to form water miscible labile zinc ammonia complex, serve as the growth cores of zinc oxide in precursor liquid;
2, get zinc metal sheet that traditional Chinese medicines buy as growth substrate, thickness is about 1mm, first carefully cleans with liquid detergent, then uses acetone and deionized water ultrasonic cleaning 8 minutes respectively, dries up with nitrogen, stand-by as growth substrate; Zinc metal sheet size does not limit, changeable, can load to reaction vessel greatly;
3, the growth substrate handled well in step 2 is directly vertically put into the precursor liquid that step 1 prepares, be placed in autoclave and tighten sealing;
4, the reactor installed in step 3 is placed in baking oven and carries out growth response at 93 DEG C, the time is 18h; At this temperature, induced growth Synthetic Routes of One-dimensional ZnO Nanorods array on the zinc metal sheet that growth cores is deposited on lattice match, finally forms large-area nanometic zinc oxide rod array;
5, after reaction terminates, the growth substrate in step 4 is taken out; Repeatedly rinse 8 minutes with deionized water, wash surface impurity off, after cleaning, nitrogen dries up, and can see that on zinc metal sheet, two sides and side have all been covered with the linen material of one deck, this material is obtained nanometic zinc oxide rod array.
embodiment 4
The method that zinc metal sheet is prepared overlarge area and high quality nanometic zinc oxide rod array of the present embodiment, concrete steps are as follows:
1, getting 0.03g (0.164mmol) zinc acetate is dissolved in 200ml deionized water, add 25ml ammoniacal liquor supersound process and carry out magnetic agitation after 4 minutes 15 minutes until zinc nitrate hexahydrate and ammoniacal liquor fully dissolve mixing, form homogeneous, stable, colourless solution, the precursor liquid needed for hydro-thermal reaction.In this precursor liquid, zinc nitrate hexahydrate and ammoniacal liquor are mixed to form water miscible labile zinc ammonia complex, serve as the growth cores of zinc oxide in precursor liquid;
2, get zinc metal sheet that traditional Chinese medicines buy as growth substrate, thickness is about 0.45mm, first carefully cleans with liquid detergent, then uses acetone and deionized water ultrasonic cleaning 20 minutes respectively, dries up with nitrogen, stand-by as growth substrate; Zinc metal sheet size does not limit, changeable, can load to reaction vessel greatly;
3, the growth substrate rolling into barrel-shape handled well in step 2 is put into the precursor liquid that step 1 prepares, be placed in autoclave and tighten sealing;
4, the reactor installed in step 3 is placed in baking oven and carries out growth response at 92 DEG C, the time is 10h; At this temperature, induced growth Synthetic Routes of One-dimensional ZnO Nanorods array on the zinc metal sheet that growth cores is deposited on lattice match, finally forms large-area nanometic zinc oxide rod array;
5, after reaction terminates, the growth substrate in step 4 is taken out; Repeatedly rinse 15 minutes with deionized water, wash surface impurity off, after cleaning, nitrogen dries up, and can see that on zinc metal sheet, two sides and side have all been covered with the linen material of one deck, this material is obtained nanometic zinc oxide rod array.
embodiment 5
The method that zinc metal sheet is prepared overlarge area and high quality nanometic zinc oxide rod array of the present embodiment, concrete steps are as follows:
1, getting 0.18g (0.981mmol) zinc acetate is dissolved in 200ml deionized water, add 10ml ammoniacal liquor supersound process and carry out magnetic agitation after 4 minutes 25 minutes until zinc nitrate hexahydrate and ammoniacal liquor fully dissolve mixing, form homogeneous, stable, colourless solution, the precursor liquid needed for hydro-thermal reaction.In this precursor liquid, zinc nitrate hexahydrate and ammoniacal liquor are mixed to form water miscible labile zinc ammonia complex, serve as the growth cores of zinc oxide in precursor liquid;
2, get zinc metal sheet that traditional Chinese medicines buy as growth substrate, thickness is about 0.05mm, first carefully cleans with liquid detergent, then uses acetone and deionized water ultrasonic cleaning 20 minutes respectively, dries up with nitrogen, stand-by as growth substrate; Zinc metal sheet size does not limit, changeable, can load to reaction vessel greatly;
3, the growth substrate rolling into barrel-shape handled well in step 2 is put into the precursor liquid that step 1 prepares, be placed in autoclave and tighten sealing;
4, the reactor installed in step 3 is placed in baking oven and carries out growth response at 94 DEG C, the time is 24h; At this temperature, induced growth Synthetic Routes of One-dimensional ZnO Nanorods array on the zinc metal sheet that growth cores is deposited on lattice match, finally forms large-area nanometic zinc oxide rod array;
5, after reaction terminates, the growth substrate in step 4 is taken out; Repeatedly rinse 15 minutes with deionized water, wash surface impurity off, after cleaning, nitrogen dries up, and can see that on zinc metal sheet, two sides and side have all been covered with the linen material of one deck, this material is obtained nanometic zinc oxide rod array.
In sum, method of the present invention is hydrothermal synthesis method, first allows zinc salt and ammonia soln be mixed to form water miscible labile zinc ammonia complex, serves as the growth cores of zinc oxide in reaction soln; At a certain temperature subsequently, induced growth Synthetic Routes of One-dimensional ZnO Nanorods array on the zinc metal sheet that growth cores is deposited on lattice match, finally forms large-area high-quality zinc oxide nano array.The inventive method is green non-poisonous, pollution-free, and repeatability is strong, and conversion unit is simple, mild condition, big area can prepare, is conducive to industrialization scale operation.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (4)
1. overlarge area prepares a method for nanometic zinc oxide rod array, it is characterized in that, comprises the steps:
A, using stand-by as growth substrate after zinc metal sheet pre-treatment;
B, described growth substrate is put into the precursor liquid of the labile zinc ammonia complex of containing water-soluble, be placed in autoclave 92 ~ 94 DEG C of sealing growth responses 8 ~ 24 hours;
C, reacted growth substrate to be taken out, cleaning, dry, the canescence material of described growth substrate surface-borne, i.e. described nanometic zinc oxide rod array;
In step B, the precursor liquid of the labile zinc ammonia complex of described containing water-soluble is dissolved in deionized water by zinc nitrate hexahydrate or zinc acetate, adds that ammoniacal liquor mixes; The zinc nitrate hexahydrate added in often liter of deionized water or zinc acetate are 0.8 ~ 5mmol, and the ammoniacal liquor added is 50 ~ 125ml; Described mixing is specially: magnetic agitation 10 ~ 30min after supersound process 3 ~ 5min;
In step B, described growth substrate vertically puts into or curlingly puts into the precursor liquid of the labile zinc ammonia complex of containing water-soluble; The large extremely described autoclave of area of described growth substrate can load.
2. overlarge area according to claim 1 prepares the method for nanometic zinc oxide rod array, it is characterized in that, in steps A, the thickness of described zinc metal sheet is 0.02 ~ 1mm.
3. overlarge area according to claim 1 prepares the method for nanometic zinc oxide rod array, it is characterized in that, in steps A, described pre-treatment is: described zinc metal sheet is first cleaned with liquid detergent, then uses acetone and deionized water ultrasonic cleaning respectively.
4. overlarge area according to claim 1 prepares the method for nanometic zinc oxide rod array, it is characterized in that, in step B, the time of described sealing growth response is 10 ~ 24 hours.
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| CN104561964B (en) * | 2014-12-24 | 2017-01-25 | 北京科技大学 | Method for preparing ZnO thin film in a controlled manner |
| CN104752070B (en) * | 2015-04-01 | 2017-09-26 | 安徽师范大学 | A kind of zinc oxide@manganese dioxide@polypyrrole ternary core-shell heterogeneous structural nanos rod array material, preparation method and applications |
| CN113720827A (en) * | 2021-08-31 | 2021-11-30 | 安徽大学 | Nano-silver modified titanium oxide nanotube array and preparation method and application thereof |
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| CN101357320A (en) * | 2008-09-18 | 2009-02-04 | 福州大学 | One-dimensional nano-array zinc oxide solid-phase micro-extraction coating and preparation method thereof |
| CN101457396B (en) * | 2007-12-14 | 2011-09-07 | 中国科学院合肥物质科学研究院 | Zinc oxide nano awl and preparation method thereof |
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| CN101457396B (en) * | 2007-12-14 | 2011-09-07 | 中国科学院合肥物质科学研究院 | Zinc oxide nano awl and preparation method thereof |
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