CN102941079B - Method for preparing photoelectric catalyst multilayer ZnO nanowire array - Google Patents
Method for preparing photoelectric catalyst multilayer ZnO nanowire array Download PDFInfo
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- CN102941079B CN102941079B CN201210438746.1A CN201210438746A CN102941079B CN 102941079 B CN102941079 B CN 102941079B CN 201210438746 A CN201210438746 A CN 201210438746A CN 102941079 B CN102941079 B CN 102941079B
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Abstract
The invention relates to a method for preparing a photoelectric catalyst multilayer ZnO nanowire array. The method is that chemical vapor deposition and a liquid phase method are adopted to be combined together, a growing method is repeated, so that the multilayer ZnO nanowire array is successfully prepared through the method for the first time. The ZnO nanowire array which is prepared through the method has high purity and does not contain metal catalyst; the ZnO nanowire array has good verticality, and a vapor phase growing part and a liquid phase growing part grow along the [0001] direction all the time; and the method has high experimental operation repeatability, can be used for preparing a ZnO nanowire array with more layers, and accordingly, the length of the ZnO nanowire array can be greatly increased.
Description
Technical field
The present invention relates to a kind of preparation method of zinc oxide nano-wire array, particularly a kind of preparation method of photoelectrocatalysis agent multilayer zinc oxide nano-wire array.
Background technology
The high speed development of day by day serious along with global problem of environmental pollution in fabrication technology, the research of the photocatalysis degradation organic contaminant of nano material becomes one of focus of the research fields such as material science, catalytic science and environmental science.ZnO is a kind of Wideband gap II-IV family semi-conducting material, band-gap energy is 3.37 eV, there is the advantages such as cheap, nontoxic, stable, in photocatalytic process, light induced electron and hole-recombination degree are less simultaneously, can issue third contact of a total solar or lunar eclipse catalytic reaction and therefore catalytic degradation toxic organic pollutant is considered to one of high-activity photocatalyst having application prospect in ultraviolet excitation condition.
Although the research about the photocatalysis degradation organic contaminant of the ZnO nano-structure of Solution Dispersion is a lot, nano particle photochemical catalyst is difficult to reclaim, and therefore catalyst recycling rate of waterused is lower.Based on the ZnO nanowire array of substrate growth, can solve the problem of catalyst recovery difficulty.2007, Huang seminar of Taiwan Tsing-Hua University carries out silica-based ZnO nanowire array the research of photocatalysis degradation organic contaminant, although the ZnO nanowire array based on silicon substrate growth has solved catalyst recovery difficulty, difficulty that recycling rate of waterused is low, but the degradation rate of this kind of method is lower, degradation rate reaches more than 90% needs 5 hours.And wherein the length of nano-wire array is the key factor that affects catalytic performance.Therefore, on silicon substrate, prepare the ZnO nanowire array of overlength, and the research that is applied to catalyze and degrade organic pollutants has great importance.
Fujishima in 1972 and Honda find at TiO
2the phenomenon of photochemical catalyzing on electrode, indicates the arrival of Multi-phase light Study of electrocatalysis New Times.In photoelectric catalysis degrading process, under alive effect, light induced electron can effectively separate with hole outside, and degradation efficiency has obtained obvious lifting.
Summary of the invention
The object of this invention is to provide a kind of multilayer zinc oxide nano-wire array preparation method with photoelectrocatalysis characteristic, the method adopts combine with liquid growth repeated growth also of chemical vapour deposition (CVD) to prepare the method for multilayer ZnO nanowire array.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for photoelectrocatalysis agent multilayer zinc oxide nano-wire array, is characterized in that the concrete steps of the method are:
A) 100 silicon chips of single-sided polishing are carried out to pretreatment;
B) two hydration zinc acetates are dissolved in ethanol and are mixed with the solution that concentration is 0.01-0.02M, be then spin-coated on step a gained silicon chip 15-20 time, dry;
C) graphite powder and zinc oxide are pressed 1:1 mass ratio grind, after it is fully mixed, adopt chemical vapour deposition technique, zinc oxide in step b gained deposition, technological parameter is: pass into argon gas and 1-2 sccm flow velocity passes into oxygen with the flow velocity of 35-70 sccm, keeping vacuum perseverance is 400 mbar, at 900-950 DEG C of temperature, be incubated 30 minutes, after temperature is down to room temperature, take out sample;
D) zinc nitrate hexahydrate and hexa are dissolved in to the mixed solution that is mixed with concentration in deionized water and is respectively 0.02-0.025 M and 0.02-0.025 M, are stirred to completely and dissolve.By step c) gained sample be suspended in above-mentioned mixed solution, 90 DEG C of reaction 1-2 hour, after reaction finishes, by deionized water sample for, ethanol cleaning post-drying;
E) repeating step c) and steps d) one to four time, finally obtain the zinc oxide nano-wire array photoelectrocatalysis agent of one deck, two-layer, three layers and four layers.
Pretreated concrete grammar described in step a is: by 100 silicon chips of single-sided polishing put into ethanol, acetone soln is ultrasonic, remove silicon chip surface organic matter, then put into the concentrated sulfuric acid, hydrogen peroxide mixed solution heats, and removes oxide, the metal impurities etc. of silicon face.Silicon chip after treatment is put into ultra-pure water ultrasonic, remove remained on surface acid solution.
The present invention adopts combine with the liquid growth repeatedly method of growth of chemical vapour deposition (CVD) to prepare the superlong ZnO nano-wire array of length up to 160 μ m first.Meanwhile, we are applied to silica-based ZnO nanowire array the research of photoelectric catalysis degrading organic dyestuff first.
In previous work, we adopt spin coating crystal seed method induction ZnO nanowire array repeatedly to grow, and the method is stricter to spin coating conditional request.In order to overcome the deficiency of spin coating crystal seed in growth course repeatedly, we carry out liquid growth at design after a chemical vapour deposition (CVD) prepares nano-wire array, the part of liquid growth is as the inducing layer of secondary vapor phase growth, substitute spin coating crystal seed layer with this, promote the gas phase of ZnO nanowire array to regrow and repeatedly growth.The length of four layers of ZnO nanowire array prepared by the method for growth of combining with liquid growth with chemical vapour deposition (CVD) has repeatedly reached 160 μ m, and this preparation method's repeatability is strong.
The method favorable repeatability, does not need catalyst and up rightness good, and the length of prepared nano wire reaches 160um.
The multilayer superlong ZnO nano-wire array that the present invention prepares, purity is high, and non-metal catalyst exists, and nano wire up rightness is good, and vapor phase growth part and liquid growth part are grown along [0001] direction all the time; The repeatability of the experimental implementation of the method is high, can prepare the ZnO nanowire array of more multi-layered number, thereby increases considerably the length of ZnO nanowire array.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention 1 adopts the chemical vapour deposition technique preparation multilayer superlong ZnO nano-wire array SEM picture that combines with liquid growth.A) individual layer ZnO nanowire array; B) double-deck ZnO nanowire array; C) three layers of ZnO nanowire array; D) four layers of ZnO nanowire array.
Fig. 2 is the XRD collection of illustrative plates of the prepared individual layer ZnO nanowire array of the embodiment of the present invention 1 and four layers of ZnO nanowire array.
Fig. 3 is ZnO nanowire array photoelectric catalysis degrading rhodamine 6G catalytic rate curve (the rhodamine 6G concentration: 10 of the prepared different numbers of plies of embodiment 1
-5mol/L).Wherein a exists without ZnO, the impact of experiment condition on rhodamine 6G; B is individual layer ZnO nanowire array; C is double-deck ZnO nanowire array; D is three layers of ZnO nanowire array.
Detailed description of the invention
After now specific embodiments of the invention being described in.
embodiment 1
The concrete preparation process of the present embodiment is as follows
(1) silicon wafer N of single-sided polishing (100) is put into ethanol, acetone soln each ultrasonic 0.5 hour, remove silicon chip surface organic matter, then put into the concentrated sulfuric acid, hydrogen peroxide (volume ratio 3:1) mixed solution, 80 DEG C are heated 1 hour, remove oxide, the metal impurities etc. of silicon face.Silicon chip after treatment is put into ultra-pure water ultrasonic 0.5 hour, remove remained on surface acid solution;
(2) take 0.1098 g bis-hydration zinc acetates and join in 25 mL ethanolic solutions, be stirred to whole dissolvings.Spin coating zinc acetate ethanolic solution 2 times on silicon chip, puts into 100 DEG C of drying boxes after each spin coating and dries 20 minutes;
(3) take 0.5 g graphite powder and 0.5 g ZnO, grind after it is fully mixed and put into quartz boat, the silicon chip (0.7 ㎝ × 1.8 ㎝) that surface is scribbled to ZnO crystal seed be placed on powder directly over, quartz boat is put into the center warm area of tube furnace.Start vavuum pump, close vavuum pump after reative cell is evacuated to vacuum state.In reative cell, pass into argon gas (flow velocity is 70 sccm) and oxygen (flow velocity is 2 sccm), in the time that vacuum reaches 400 mbar in reative cell, again start vavuum pump, guarantee that in reative cell, vacuum perseverance is 400 mbar.Start temperature elevation system, be incubated 30 minutes after rising to 950 DEG C with 24 DEG C/min.Keep gas flow rate constant, after tube furnace temperature is down to room temperature, take out sample;
(4) take 1.8593 g zinc nitrate hexahydrate (Zn (NO
3)
26H
2o) and 0.8762 g hexa (HMTA), joins in 500 mL deionized waters, is stirred to completely and dissolves.The sample preparing is faced down and is suspended in above-mentioned mixed solution, and 90 DEG C are reacted 2 hours.After reaction finishes, the baking oven of deionized water, ethanol for sample being put into 60 DEG C after cleaning is dried;
(5) repeating step three and step 4, preparation multilayer ZnO nanowire array.
In above-described embodiment the structure of prepared sample and pattern characterize with and PhotoelectrocatalytiPerformance Performance test, its result is as follows:
1, Fig. 1 is that and liquid growth combines and the SEM of different number of plies ZnO nanowire arrays prepared by the method for repeated growth schemes in employing chemical vapour deposition (CVD).As seen from the figure, along with the increase of growth number of times, the number of plies of prepared ZnO nanowire array constantly increases, and the length of nano-wire array is in continuous increase, and the length of four layers of ZnO nanowire array reaches 160 μ m.
2, X-ray diffraction analysis (XRD) is to different number of plies ZnO nanowire array structural analysis (see figure 2)s, and from collection of illustrative plates, individual layer is consistent with the diffraction maximum of the ZnO nanowire array of four layers, is hexagonal wurtzite ZnO crystal, and free from admixture peak occurs.
3, photocatalysis performance test.The silica-based ZnO nanowire array of the prepared different numbers of plies is applied to the research of photoelectric catalysis degrading rhodamine 6G.As shown in Fig. 3, when three layers of ZnO nanowire array photoelectric catalysis degrading rhodamine 6G 40 min, degraded effect reaches 97 %, and compared with individual layer ZnO nanowire array, degradation rate has promoted 56%.Multilayer ZnO nanowire array is because length is significantly improved, and surface area increases, thereby the adsorbance of dyestuff increases.The PhotoelectrocatalytiPerformance Performance of multilayer ZnO nanowire array has obtained obvious lifting compared with the PhotoelectrocatalytiPerformance Performance of individual layer ZnO nanowire array.
Claims (2)
1. a preparation method for photoelectrocatalysis agent multilayer zinc oxide nano-wire array, is characterized in that the concrete steps of the method are:
A) 100 silicon chips of single-sided polishing are carried out to pretreatment;
B) two hydration zinc acetates are dissolved in ethanol and are mixed with the solution that concentration is 0.01-0.02M, be then spin-coated on step a) gained silicon chip 15-20 time, dry;
C) graphite powder and zinc oxide are pressed 1:1 mass ratio grind, after it is fully mixed, adopt chemical vapour deposition technique, on step b) gained silicon chip, deposit zinc oxide, technological parameter is: pass into argon gas and 1-2 sccm flow velocity passes into oxygen with the flow velocity of 35-70 sccm, keeping vacuum perseverance is 400 mbar, at 900-950 DEG C of temperature, be incubated 30 minutes, after temperature is down to room temperature, take out sample;
D) zinc nitrate hexahydrate and hexa are dissolved in to the mixed solution that is mixed with concentration in deionized water and is respectively 0.02-0.025 M and 0.02-0.025 M, are stirred to completely and dissolve; By step c) gained sample be suspended in above-mentioned mixed solution, 90 DEG C of reaction 1-2 hour, after reaction finishes, by deionized water sample for, ethanol cleaning post-drying;
E) repeating step c) and steps d) one to four time, finally obtain zinc oxide nano-wire array photoelectrocatalysis agent two-layer, three layers, four layers or five layers.
2. the preparation method of photoelectrocatalysis agent multilayer zinc oxide nano-wire array according to claim 1, it is characterized in that the pretreated concrete grammar described in step a is: by 100 silicon chips of single-sided polishing put into ethanol, acetone soln is ultrasonic, remove silicon chip surface organic matter, then put into the concentrated sulfuric acid, hydrogen peroxide mixed solution heats, and removes oxide, the metal impurities of silicon face; Silicon chip after treatment is put into ultra-pure water ultrasonic, remove remained on surface acid solution.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618738A (en) * | 2003-11-18 | 2005-05-25 | 北京大学 | Zinc oxide nano-wire and its preparation method and application |
| CN1674230A (en) * | 2004-03-26 | 2005-09-28 | 北京大学 | Silicon substrate nano-zinc oxide and producing method and application thereof |
| CN1800029A (en) * | 2005-12-30 | 2006-07-12 | 北京科技大学 | Ultra-fine zinc oxide nonometer line and its preparation method |
| GB2469869A (en) * | 2009-05-01 | 2010-11-03 | Univ Bolton | Continuous ZnO films |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618738A (en) * | 2003-11-18 | 2005-05-25 | 北京大学 | Zinc oxide nano-wire and its preparation method and application |
| CN1674230A (en) * | 2004-03-26 | 2005-09-28 | 北京大学 | Silicon substrate nano-zinc oxide and producing method and application thereof |
| CN1800029A (en) * | 2005-12-30 | 2006-07-12 | 北京科技大学 | Ultra-fine zinc oxide nonometer line and its preparation method |
| GB2469869A (en) * | 2009-05-01 | 2010-11-03 | Univ Bolton | Continuous ZnO films |
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