CN104549209A - Double-faced zinc oxide nanoarray photocatalytic material and preparation method thereof - Google Patents
Double-faced zinc oxide nanoarray photocatalytic material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a double-faced zinc oxide nanoarray photocatalytic material and a preparation method thereof. The double-faced zinc oxide nanoarray photocatalytic material comprises ZnO nanoarrays and a quartz substrate, wherein the ZnO nanoarrays grow on two surfaces of the whole quartz substrate. The preparation method comprises the following steps: preparing a layer of a ZnO film on each of the two surfaces of the cleaned quartz substrate as a crystal seed layer respectively; simultaneously growing the ZnO nanoarrays on the two surfaces of the quartz substrate by utilizing a hydrothermal method. The double-faced ZnO nanoarrays are prepared on the quartz substrate through the hydrothermal method, so that the utilization rate of sunlight can be effectively increased and the photocatalytic performance can be remarkably improved. The preparation method has the advantages of simplicity of operation, strong controllability, low cost and the like, is suitable for large-area growth, and has a very high application value and a good application prospect; a catalyst is convenient to recover and reusable.
Description
Technical field
The invention belongs to the technical field of catalysis material and preparation thereof, relate to a kind of catalysis material based on two-sided ZnO nano array and preparation method thereof.
Background technology
Along with developing rapidly of modern industry, the contour toxic pollutant of sewage, waste gas and byproduct of reaction produces in a large number, and problem of environmental pollution is day by day serious.The sunshine that semiconductor catalyst can make full use of " cheap, green ", the various toxic pollutant of effective catalytic degradation is the important channel solving the deterioration of global environment.
Zinc oxide (ZnO) is the semi-conducting material that one has wide direct band gap (3.37eV) and high exciton bind energy (60meV), there is high electron transfer rate and longer electron lifetime, its structure comparison of nanoscale ZnO enriches and is easy to controllable growth, makes it be with a wide range of applications in photocatalysis degradation organic contaminant.
But the suspended phase Photocatalytic Oxidation With Semiconductors method be widely used at present, also exist photochemical catalyst easily condense, with the shortcoming such as shipwreck is separated, make catalyst be difficult to reclaim and recycling.Catalyst immobilization can overcome above-mentioned deficiency effectively.In existing research report, just catalysis material is fixed on the one side of carrier, carrier another side is then ignored for a long time, is not utilized effectively.Quartz glass has high temperature tolerance, and the optical property of fabulous chemical stability, particularly quartz glass has its distinctive feature, and it is the most the superior of all ultraviolet light materials, can pass through again visible ray and near infrared light.And quartzy resource is very abundant at China's reserves, cheap, be easy to industrialization.Thus quartz glass can as the desirable supporting substrate of nano-ZnO.For improving the utilization rate to light, improving photocatalysis performance, quartz substrate being prepared two-sided ZnO nano array there is very high using value.But prepare research and the method for two-sided ZnO nano array photochemical catalyst in quartz substrate, there is not been reported.
Summary of the invention
The object of this invention is to provide a kind of two-sided zinc oxide nano array catalysis material and the preparation method that can be applicable to photocatalysis field, utilize the light transmission of quartz substrate excellence, quartz substrate is prepared two-sided ZnO nano array, absorbing light can be improved, improve photocatalysis performance, carry out the research of photocatalysis performance, shown that there is good application prospect in photocatalysis to degrade organic matter.
The object of the invention is to be achieved through the following technical solutions:
A kind of two-sided ZnO nano array catalysis material, be made up of ZnO nano array and quartz substrate, described quartz substrate is the quartz glass with high light transmittance, and ZnO nano array vertically grows two surfaces in whole quartz substrate.
The present invention utilizes hydrothermal synthesis method to synthesize ZnO nano post, rod, line, and making ZnO nano-array-quartz substrate-ZnO nano array, concrete technical scheme is as follows:
One, crystal seed layer is prepared: prepare layer of ZnO film respectively as crystal seed layer on two surfaces of the quartz substrate cleaned up.
In this step, the cleaning method of described quartz substrate is: by quartz substrate each ultrasonic cleaning 10 ~ 20 minutes in acetone and absolute ethyl alcohol respectively, use deionized water ultrasonic cleaning again 10 ~ 20 minutes, after quartz substrate is reversed, repeat above-mentioned cleaning process, again quartz substrate is vertically placed in the solution, by above-mentioned cleaning method cleaning 1 ~ 2 time, finally dried up.
In this step, use magnetically controlled sputter method making ZnO film.
In this step, the thickness of described ZnO film is 10 ~ 100nm.
Two, hydro-thermal method is utilized to prepare two-sided ZnO nano array: to pour in the polytetrafluoroethyllining lining of reactor by the mixed aqueous solution of the molar concentration zinc acetates such as containing of preparing and hexamethylenetetramine, the quartz substrate of ZnO crystal seed layer is had vertically to put into the solution of reactor on the two sides of above-mentioned preparation, sealed reactor also puts into heated at constant temperature drying box, at 70 ~ 100 DEG C, be incubated 2 ~ 24 hours; Be down to room temperature, by two surfaces all length have the quartz glass of ZnO nano array to take out, with deionized water rinsing, natural drying in atmosphere, the catalysis material of obtained ZnO nano array-quartz substrate-ZnO nano array structure.
In this step, described ZnO nano array is ZnO nano post, ZnO nanorod or ZnO nanowire array structure.
In this step, the compactedness of described mixed aqueous solution in polytetrafluoroethyllining lining is 60 ~ 80vol.%.
In this step, the concentration of described mixed aqueous solution is 0.01 ~ 0.2mol/L.
The present invention's two-sided ZnO nanorod (post, line) array that utilized hydro-thermal method to synthesize in quartz substrate, prepare ZnO nano array-quartz substrate-ZnO nano array structured light catalyst, effectively can improve the utilization rate of sunshine, significantly improve photocatalysis performance.Its preparation method has that simple to operate, controllability is strong, low cost and other advantages, be applicable to large area deposition, and catalyst is convenient to reclaim, reusable, has very high practical value and application prospect.ZnO nano array-quartz substrate-ZnO nano array structured light catalysis material effectively can utilize substrate, fully absorb sunshine, significantly improve photocatalysis performance.ZnO nano array load on the quartz glass of stable chemical performance, be convenient to reclaim and reuse, and ZnO and quartz at China's rich reserves, for large-scale production and application, there is good DEVELOPMENT PROSPECT.
Accompanying drawing explanation
Fig. 1 is the transmitted light spectrogram of quartz substrate;
Fig. 2 is the XRD collection of illustrative plates of two-sided ZnO nano-rod array prepared by hydro-thermal method;
Fig. 3 is the SEM top view of two-sided ZnO nano-rod array prepared by hydro-thermal method;
Fig. 4 is the SEM sectional view of two-sided ZnO nano-rod array prepared by hydro-thermal method;
Fig. 5 is two-sided ZnO nano array catalysis material curve map to methyl orange solution degraded under UV-irradiation.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1: the preparation of two-sided ZnO nano-rod array in quartz substrate.
One, substrate cleaning: quartz substrate selects size to be l × lcm
2, thickness 1mm quartz glass, each ultrasonic cleaning 10 minutes in acetone and absolute ethyl alcohol respectively, use deionized water ultrasonic cleaning again 10 minutes, after quartz substrate is reversed, repeat above-mentioned cleaning process, then quartz substrate is vertically placed, at by acetone, absolute ethyl alcohol and deionized water ultrasonic 10 minutes, make substrate two surfaces completely clean, finally dried up.
Two, two-sided crystal seed layer preparation: adopt radiofrequency magnetron sputtering technology, the quartz substrate cleaned up be fixed on the sample stage of r. f. magnetron sputtering equipment, with mechanical pump and molecular pump to vacuum chamber, when vacuum reaches 2 × 10
-3during Pa, pass into the mist of high-purity argon gas and oxygen, adjusting gas flow meter makes the flow-rate ratio of oxygen, argon gas be 3:7, and adjustment pressure in vacuum tank is 1Pa, and radio-frequency sputtering power is 100W.The ZnO crystal seed layer that sputtering 10nm is thick, takes out quartz substrate, quartz substrate is reversed, retightened on sample stage, once sputter experiment again according to described method just now, prepare the ZnO crystal seed layer of same thickness at the another side of quartz substrate.
Three, two-sided ZnO nano-rod array preparation: prepare zinc acetate and hexamethylenetetramine solution that 15mL concentration is 0.05mol/L respectively, the two mix and blend was poured in the polytetrafluoroethyllining lining of 1 50mL reactor after 10 minutes.Clamping there being the quartz substrate specimen holder of two-sided ZnO crystal seed layer in above-mentioned preparation vertically puts into wherein, put it into after tightening in drying box, then be warmed up to 95 DEG C, constant temperature keeps 24 hours, is turned off by drying box power supply afterwards, naturally cool to room temperature, then sample is taken out, and surperficial with deionized water rinsing, then natural drying in atmosphere, obtain two-sided ZnO nano-rod array, and can be used as catalysis material.
The transmitted spectrum of the present embodiment quartz substrate used is shown in Fig. 1, selected substrate has good light transmission, the XRD spectra preparing sample is shown in Fig. 2, SEM shape appearance figure as shown in Figure 3, ZnO nanorod homoepitaxial is in quartz substrate surface, and the average diameter of nanometer rods is about 200 nm, can see from sectional view 4, the two sides of quartz substrate all grows and has ZnO nano array, and the length of nanometer rods is basically identical.
Embodiment 2: two-sided ZnO nano-rod array photocatalysis performance test.
The two-sided ZnO nano-rod array obtained in example 1 is carried out the research of Photocatalytic Degradation On Methyl Orange Solution, radiation source is solar simulator (500W xenon lamp).Detailed process is: be 1cm by area
2sample vertically put into methyl orange solution, irradiate solution and sample surfaces with analog light source, the time is 150 minutes, at regular intervals, takes out part methyl orange solution, tests its absorbance by ultraviolet specrophotometer.In order to compare the photocatalysis effect of bilateral structure catalysis material, also photocatalysis test is carried out to the one side ZnO nano-rod array obtained in quartz substrate under similarity condition.As shown in Figure 5, compared with one side ZnO nano array, the two-sided ZnO nano array under equal conditions shows more excellent photocatalysis performance to result.
Embodiment 3: the preparation of two-sided ZnO nanowire array.
The concentration of the zinc acetate in embodiment 1 and hexamethylenetetramine solution is changed into 0.01mol/L, and other concrete steps are with embodiment 1.Obtain the two-sided ZnO nanowire array that average diameter is 20nm.
Embodiment 4: the preparation of two-sided ZnO nano post array.
The concentration of the zinc acetate in embodiment 1 and hexamethylenetetramine solution is set as 0.2mol/L, and growth time is 4 hours, and other concrete steps are with embodiment 1.Obtain the two-sided ZnO nano post array that average diameter is about 650nm.
Claims (9)
1. a two-sided zinc oxide nano array catalysis material, is characterized in that described catalysis material is made up of ZnO nano array and quartz substrate, and ZnO nano array growth is on two surfaces of whole quartz substrate.
2. two-sided zinc oxide nano array catalysis material according to claim 1, is characterized in that described ZnO nano array is ZnO nano post, ZnO nanorod or ZnO nanowire array structure.
3. a preparation method for two-sided zinc oxide nano array catalysis material, is characterized in that described method step is as follows:
One, layer of ZnO film is prepared respectively as crystal seed layer on two surfaces of the quartz substrate cleaned up;
Two, the mixed aqueous solution of the molar concentration zinc acetates such as containing of preparing and hexamethylenetetramine is poured in the polytetrafluoroethyllining lining of reactor, the quartz substrate of ZnO crystal seed layer is had on two sides vertically to put into the solution of reactor, sealed reactor also puts into heated at constant temperature drying box, at 70 ~ 100 DEG C, be incubated 2 ~ 24 hours; Be down to room temperature, by two sides all length have the quartz glass of ZnO nano array to take out, with deionized water rinsing, natural drying in atmosphere, the catalysis material of obtained ZnO nano array-quartz substrate-ZnO nano array structure.
4. the preparation method of two-sided zinc oxide nano array catalysis material according to claim 3, it is characterized in that the cleaning method of described quartz substrate is: by quartz substrate each ultrasonic cleaning 10 ~ 20 minutes in acetone and absolute ethyl alcohol respectively, use deionized water ultrasonic cleaning again 10 ~ 20 minutes, after quartz substrate is reversed, repeat above-mentioned cleaning process, again quartz substrate is vertically placed in the solution, by above-mentioned cleaning method cleaning 1 ~ 2 time, finally dried up.
5. the preparation method of two-sided zinc oxide nano array catalysis material according to claim 3, is characterized in that using magnetically controlled sputter method to prepare two-sided ZnO film.
6. the preparation method of the two-sided zinc oxide nano array catalysis material according to claim 3 or 5, is characterized in that the thickness of described ZnO film is 10 ~ 100nm.
7. the preparation method of two-sided zinc oxide nano array catalysis material according to claim 3, is characterized in that the compactedness of described mixed aqueous solution in polytetrafluoroethyllining lining is 60 ~ 80vol.%.
8. the preparation method of the two-sided zinc oxide nano array catalysis material according to claim 3 or 7, is characterized in that the concentration of described mixed aqueous solution is 0.01 ~ 0.2mol/L.
9. the preparation method of two-sided zinc oxide nano array catalysis material according to claim 3, is characterized in that described ZnO nano array is ZnO nano post, ZnO nanorod or ZnO nanowire array structure.
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Cited By (5)
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| CN106423131A (en) * | 2016-10-09 | 2017-02-22 | 全普光电科技(上海)有限公司 | Transparent photocatalytic thin film, preparation method and semiconductor device |
| CN107020055A (en) * | 2017-06-10 | 2017-08-08 | 安徽工程大学 | A kind of SiO2The preparation method and applications of@ZnO core shell structure polypody bead nano composite materials |
| CN107983327A (en) * | 2017-12-01 | 2018-05-04 | 西安理工大学 | A kind of method for improving ZnO nano-rod array photocatalysis performance |
| CN109608054A (en) * | 2018-12-28 | 2019-04-12 | 株洲电力机车广缘科技有限责任公司 | A kind of preparation method of zinc oxide nano-wire array |
| CN110970579A (en) * | 2018-09-30 | 2020-04-07 | 纳晶科技股份有限公司 | Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423131A (en) * | 2016-10-09 | 2017-02-22 | 全普光电科技(上海)有限公司 | Transparent photocatalytic thin film, preparation method and semiconductor device |
| CN107020055A (en) * | 2017-06-10 | 2017-08-08 | 安徽工程大学 | A kind of SiO2The preparation method and applications of@ZnO core shell structure polypody bead nano composite materials |
| CN107983327A (en) * | 2017-12-01 | 2018-05-04 | 西安理工大学 | A kind of method for improving ZnO nano-rod array photocatalysis performance |
| CN107983327B (en) * | 2017-12-01 | 2020-08-18 | 西安理工大学 | Method for improving photocatalytic performance of ZnO nanorod array |
| CN110970579A (en) * | 2018-09-30 | 2020-04-07 | 纳晶科技股份有限公司 | Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device |
| CN110970579B (en) * | 2018-09-30 | 2022-12-02 | 纳晶科技股份有限公司 | Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device |
| CN109608054A (en) * | 2018-12-28 | 2019-04-12 | 株洲电力机车广缘科技有限责任公司 | A kind of preparation method of zinc oxide nano-wire array |
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Application publication date: 20150429 |