CN101774537B - A preparation method of TiO2-coated ZnO nanorod arrays grown vertically in microchannels - Google Patents
A preparation method of TiO2-coated ZnO nanorod arrays grown vertically in microchannels Download PDFInfo
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- 239000002073 nanorod Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 6
- 238000003491 array Methods 0.000 title abstract 5
- 239000000243 solution Substances 0.000 claims abstract description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000006210 lotion Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- -1 01M zinc salt Chemical class 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 238000000520 microinjection Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
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- 230000008901 benefit Effects 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000013904 zinc acetate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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Abstract
一种微通道垂直生长TiO2包覆ZnO纳米棒阵列的制备方法。包括：以玻璃毛细管为微通道，首先清洗微通道；配制0.001～0.01M锌盐的醇溶液，0.004～0.04M碱的醇溶液，利用微注射泵将其同时输送到置于烘箱中的微通道中，在微通道内表面上得到一层ZnO晶种薄膜；然后配制0.025～2M的锌盐溶液，0.025～2M的胺溶液，同时输送到置于烘箱中且内表面预制有ZnO晶种的微通道中制备垂直生长的ZnO纳米棒阵列；最后向垂直生长有ZnO纳米棒阵列的微通道中输送浓度为3～5mg/mL，pH为3.8～4.2的TiO2溶胶，在微通道内表面上得到垂直生长的TiO2包覆ZnO纳米棒阵列。
A preparation method for microchannel vertical growth of TiO2 - coated ZnO nanorod arrays. Including: use the glass capillary as the microchannel, first clean the microchannel; prepare 0.001-0.01M zinc salt alcohol solution, 0.004-0.04M alkali alcohol solution, and use the micro-injection pump to simultaneously transport them to the microchannel placed in the oven In the process, a layer of ZnO seed crystal film is obtained on the inner surface of the microchannel; then a 0.025-2M zinc salt solution and a 0.025-2M amine solution are prepared and transported to the microchannel in an oven with ZnO seed crystals prefabricated on the inner surface. The vertically grown ZnO nanorod arrays were prepared in the channel; finally, the TiO 2 sol with a concentration of 3-5 mg/mL and a pH of 3.8-4.2 was delivered to the microchannel with the vertically grown ZnO nanorod arrays, and obtained on the inner surface of the microchannel. Vertically grown TiO2 coated ZnO nanorod arrays.
Description
Technical field
The invention belongs to nanometer technology and microflow control technique crossing domain, particularly relate to vertical-growth TiO on the inner surface of a kind of microchannel
2The preparation method of clading ZnO nano rod array.
Background technology
Utilize semiconductor nano material such as TiO
2, the photocatalysis degradation organic contaminant such as ZnO and light decomposition water caused people's very big research interest, yet in actual applications, separation and the regeneration of nanocatalyst from reactant liquor is to limit its widely used one large problem.For addressing this problem, some researchers once attempted nanocatalyst such as TiO
2Nano particle is fixed in the various loads (such as fiber, Al
2O
3Substrate etc.), still but greatly reduce like this solid-liquid contact area of catalyst and reactant liquor.Another main cause that affects in addition conductor photocatalysis efficient is the compound fast of photo-generated carrier, and people propose to utilize the coupling semiconductor to realize separating of electronics and hole for this reason.It is reported TiO
2/ ZnO coupling nano particle has demonstrated than simple TiO
2The photocatalysis performance that perhaps ZnO is stronger (J.Phys.Chem.B 105 (2001) 1033-1040), and monodimension nanometer material such as ZnO nano-wire (J.Phys.Chem.C 112 (2008) 8850-8855), four jiaos of ZnO nanorods (J.Cryst.Growth 311 (2009) 1378-1384) etc. also demonstrate stronger photocatalysis performance.And nanorod structure is fixed on the particular substrate and does not have appreciable impact to reducing the solid-liquid contact area, therefore TiO
2It will be the good photochemical catalyst with high catalytic activity that people expect that the ZnO nanorod that nano particle coats is fixed in the substrate.
The microminiaturization of chemical reaction is a main trend of chemical technology field in recent years.Microreactor based on the microchannel has demonstrated huge advantage than the popular response device, such as high specific area, fast heat and quality transmission etc., makes it in continuous light catalytic reaction and the fields such as organic synthesis and biological medicine widely application prospect arranged.With TiO
2The ZnO nanorod vertical-growth that coats will be very significant on the inner surface of microchannel.At first one-dimensional nano structure will greatly increase the specific area of microchannel; If separating after secondly will avoiding reunion that nanocatalyst in use causes and use as photocatalysis microreactor, and will realize rapidly, continuously photocatalytic process by the inherent advantage of microreactor; Last nanometer semiconductor structure more fixing other functionalized designs that will realize micro-fluidic device on the inner surface of microchannel are as can be by the photocatalysis cleaning by the microchannel of Organic Pollution, especially for reusing of the microchannel of organic synthesis.
The present invention aims to provide a kind of novel vertical-growth TiO on the inner surface of microchannel
2The preparation method of clading ZnO nano rod array.This method combines the preparation of monodimension nanometer material and modification, the modification of microfluidic channel, make every effort to design for light-catalysed microreactor rapidly, continuously, and this method process simple, expend littlely, the newest research results of combining nano science and technology will promote the functionalized design based on the micro-/ nano device of microchannel greatly.
Summary of the invention
The object of the present invention is to provide a kind of micro-channel vertical-growth TiO
2Clading ZnO (TiO
2/ ZnO) the preparation method of nanometer stick array.
The invention provides a kind of microchannel vertical centering control growth TiO
2The preparation method of clading ZnO nano rod array comprises:
(1) cleaning of microchannel
With capillary glass tube as the microchannel, the microchannel is soaked among the washing lotion I at 110～130 ℃ of lower 10～30min, behind the deionized water rinsing, again the microchannel is soaked among the washing lotion II at 60～80 ℃ of lower 10～30min of immersion, at last with also oven dry behind the deionized water rinsing;
(2) ZnO crystal seed layer thin film technology on the inner surface of microchannel
The alcoholic solution of preparation 0.001～0.01M zinc salt, 0.004～0.04M alkali alcosol, two solution suck respectively the syringe of two 10mL, it is 5～50 μ L/min that the setting micro syringe pump pushes away speed, two solution are transported to simultaneously the microchannel that places in advance 30～80 ℃ of baking ovens, fluid stops to carry after filling with the microchannel, oven temperature is increased to 150～200 ℃ of annealing, time 1～2h, successively utilize absolute ethyl alcohol, washed with de-ionized water microchannel, and at 150～160 ℃ of lower oven dry 1～2h, obtain ZnO crystal seed layer film at the microchannel inner surface;
(3) preparation of orthotropic ZnO nano-rod array on the inner surface of microchannel
The zinc solution of preparation 0.025～2M, 0.025 the amine aqueous solution of～2M, two solution suck respectively the syringe of two 10mL, it is 5～50 μ L/min that the setting micro syringe pump pushes away speed, two solution are transported in the microchannel that is shaped with in advance the ZnO crystal seed simultaneously, behind 85～120 ℃ of lower reaction 60～120min, stop delivered solution in the baking oven, with the washed with de-ionized water microchannel and at 150～200 ℃ of lower oven dry 1～2h, obtain orthotropic ZnO nano-rod array on the inner surface of microchannel;
(4) vertical-growth TiO on the inner surface of microchannel
2The preparation of clading ZnO nano rod array
Be 3～5mg/mL with concentration, pH is 3.8～4.2 TiO
2Colloidal sol sucks in the syringe of 10mL and is transported in the long microchannel that ZnO nano-rod array arranged of inner surface with micro syringe pump and coats, after colloidal sol is full of the microchannel, stop to carry, and the microchannel is placed 80～90 ℃ of baking oven 10～12h, obtain orthotropic TiO on the inner surface
2Clading ZnO nano rod array.
Described step (1) washing lotion I component is the concentrated sulfuric acid, hydrogen peroxide and distilled water, and its volume ratio satisfies V
The concentrated sulfuric acid: V
Hydrogen peroxide: V
Distilled water=4: 1: 20, washing lotion II component was ammoniacal liquor, hydrogen peroxide and distilled water, and its volume ratio satisfies V
Ammoniacal liquor: V
Hydrogen peroxide: V
Distilled water=1: 4: 20.
Zinc salt in described step (2) or the step (3) is zinc acetate, zinc sulfate, zinc chloride or zinc nitrate, preferred zinc acetate or zinc nitrate.
Alkali in the described step (2) is alkali metal hydroxide, ammoniacal liquor, urea or hydrazine hydrate, preferred NaOH.
Alcohol in the described step (2) is methyl alcohol or ethanol, preferred alcohol.
Amine in the described step (3) is hexa or diethylenetriamine, preferred hexa.
TiO in the described step (4)
2The Sol-gel Coated number of times can be 1～4 time, can be little by the coating number of times of control colloidal sol
Obtain TiO orthotropic, optimum profile on the channel inner surface
2Clading ZnO nano rod array.
Beneficial effect
(1) preparation of monodimension nanometer material and modification, the modification of microfluidic channel are combined, the inner surface in the microchannel has obtained TiO
2Clading ZnO nano rod array has increased the specific area of microchannel inner surface greatly;
(2) be expected to for the design photocatalysis with microchannel type reactor, avoid the reunion that nanocatalyst in use causes and solve the problem that nanocatalyst separates time and effort consuming, realize carrying out continuously of light-catalyzed reaction.
Description of drawings
The field emission scanning electron microscope photo of the ZnO nano-rod array on the inner surface of Fig. 1 microchannel: a) the nanometer stick array photo of inclination certain angle, b) cross-sectional picture of nanometer stick array;
TiO on the inner surface of Fig. 2 microchannel
2The field emission scanning electron microscope photo of/ZnO nano-rod array (collosol concentration is 5mg/mL, coats 1 time);
TiO on the inner surface of Fig. 3 microchannel
2The transmission electron microscope photo of/ZnO nano-rod array (collosol concentration is 5mg/mL, coats 2 times): a) low power transmission electron microscope photo, b) high-resolution-ration transmission electric-lens photo;
TiO on the inner surface of Fig. 4 microchannel
2The field emission scanning electron microscope photo of/ZnO nano-rod array (collosol concentration is 4mg/mL, coats 3 times);
TiO on the inner surface of Fig. 5 microchannel
2The field emission scanning electron microscope photo of/ZnO nano-rod array (collosol concentration is 3mg/mL, coats 4 times).
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Preparation washing lotion I (V
The concentrated sulfuric acid: V
Hydrogen peroxide: V
Distilled water=4: 1: 20) and washing lotion II (V
Ammoniacal liquor: V
Hydrogen peroxide: V
Distilled water=1: 4: 20).The microchannel is soaked among the washing lotion I at 110 ℃ of lower 10min, behind the deionized water rinsing, again the microchannel is soaked among the washing lotion II at 70 ℃ of lower 10min of immersion, at last with behind the deionized water rinsing, dry for standby.The Zinc diacetate dihydrate ethanolic solution of preparation 0.01M, the NaOH ethanolic solution of 0.04M, the zinc nitrate hexahydrate solution of 0.05M, the hexa solution of 0.05M.Zinc diacetate dihydrate ethanolic solution and NaOH ethanolic solution are sucked respectively the syringe of two 10mL, it is 25 μ L/min that the setting micro syringe pump pushes away speed, it is transported to the microchannel that places in advance 60 ℃ of baking ovens simultaneously, stop to carry after filling with the microchannel, behind the reaction 2h oven temperature is increased to 150 ℃ of annealing, time 1h.Successively utilize ethanol, washed with de-ionized water microchannel, and 150 ℃ of lower oven dry, obtain ZnO crystal seed layer film at the microchannel inner surface.Utilize subsequently micro syringe pump that zinc nitrate hexahydrate solution and hexa solution are transported in the microchannel of existing ZnO crystal seed simultaneously, after reacting 2h under 90 ℃ in the baking oven, stop delivered solution, clean the microchannel and at 150 ℃ of lower oven dry 1h, obtain orthotropic ZnO nano-rod array at the microchannel inner surface.At last with the TiO of 5mg/mL
2Colloidal sol is filled with the microchannel 1 time that the length that places 80 ℃ of baking ovens has ZnO nanorod with micro syringe pump, keeps temperature 10h, obtains orthotropic TiO at the microchannel inner surface
2/ ZnO nano-rod array.Fig. 1 is the field emission scanning electron microscope photo of the ZnO nano-rod array on the inner surface of microchannel that obtains of the present embodiment, and can find out: the ZnO nano-rod array vertical-growth is (Fig. 1 b) on the inner surface of microchannel, and is evenly distributed that (Fig. 1 a).Orthotropic TiO on the microchannel inner surface that Fig. 2 obtains for this example
2The field emission scanning electron microscope photo of/ZnO nano-rod array is compared TiO with pure ZnO nanorod
2The nanorod surfaces that coats becomes slightly coarse and diameter slightly becomes large.
Embodiment 2
Preparation washing lotion I (V
The concentrated sulfuric acid: V
Hydrogen peroxide: V
Distilled water=4: 1: 20) and washing lotion II (V
Ammoniacal liquor: V
Hydrogen peroxide: V
Distilled water=1: 4: 20).The microchannel is soaked among the washing lotion I at 110 ℃ of lower 30min, behind the deionized water rinsing, again the microchannel is soaked among the washing lotion II at 60 ℃ of lower 30min of immersion, behind the last deionized water rinsing, dry for standby.The Zinc diacetate dihydrate ethanolic solution of preparation 0.01M, the NaOH ethanolic solution of 0.04M, the zinc nitrate hexahydrate solution of 0.025M, the hexa solution of 0.025M.Zinc diacetate dihydrate ethanolic solution and NaOH ethanolic solution are sucked respectively the syringe of two 10mL, it is 50 μ L/min that the setting micro syringe pump pushes away speed, it is transported to the microchannel that places in advance 30 ℃ of baking ovens simultaneously, stop to carry after filling with the microchannel, behind the reaction 1h oven temperature is increased to 180 ℃ of annealing, time 1h.Successively utilize ethanol, washed with de-ionized water microchannel, and 150 ℃ of lower oven dry, obtain ZnO crystal seed layer film at the microchannel inner surface.Utilize subsequently micro syringe pump that zinc nitrate hexahydrate solution and hexa solution are transported in the microchannel of existing ZnO crystal seed simultaneously, after reacting 2h under 85 ℃ in the baking oven, stop delivered solution, clean the microchannel and at 160 ℃ of lower oven dry 1.5h, obtain orthotropic ZnO nano-rod array at the microchannel inner surface.At last with the TiO of 5mg/mL
2Colloidal sol is filled with the microchannel 2 times that the length that places 80 ℃ of baking ovens has ZnO nanorod with micro syringe pump, keeps temperature 10h, obtains orthotropic TiO at the microchannel inner surface
2/ ZnO nano-rod array.Orthotropic TiO on the microchannel inner surface that Fig. 3 obtains for this example
2The transmission electron microscope photo of/ZnO nano-rod array (Fig. 3 a) and high-resolution-ration transmission electric-lens photo (Fig. 3 b), has coated TiO around can seeing ZnO nanorod
2Nano particle.
Embodiment 3
Preparation washing lotion I (V
The concentrated sulfuric acid: V
Hydrogen peroxide: V
Distilled water=4: 1: 20) and washing lotion II (V
Ammoniacal liquor: V
Hydrogen peroxide: V
Distilled water=1: 4: 20).The microchannel is soaked among the washing lotion I at 130 ℃ of lower 10min, behind the deionized water rinsing, again the microchannel is soaked among the washing lotion II at 80 ℃ of lower 10min of immersion, behind the last deionized water rinsing, dry for standby.The Zinc diacetate dihydrate ethanolic solution of preparation 0.001M, the NaOH ethanolic solution of 0.004M, the zinc nitrate hexahydrate solution of 1M, the hexa solution of 1M.Zinc diacetate dihydrate ethanolic solution and NaOH ethanolic solution are sucked respectively the syringe of two 10mL, it is 10 μ L/min that the setting micro syringe pump pushes away speed, it is transported to the microchannel that places in advance 80 ℃ of baking ovens simultaneously, stop to carry after filling with the microchannel, behind the reaction 2h oven temperature is increased to 150 ℃ of annealing, time 2h.Successively utilize ethanol, washed with de-ionized water microchannel, and 150 ℃ of lower oven dry, obtain ZnO crystal seed layer film at the microchannel inner surface.Utilize subsequently micro syringe pump that zinc nitrate hexahydrate solution and hexa solution are transported in the microchannel of existing ZnO crystal seed simultaneously, after reacting 1h under 120 ℃ in the baking oven, stop delivered solution, clean the microchannel and at 150 ℃ of lower oven dry 2h, obtain orthotropic ZnO nano-rod array at the microchannel inner surface.At last with the TiO of 4mg/mL
2Colloidal sol is filled with the microchannel 3 times that the length that places 90 ℃ of baking ovens has ZnO nanorod with micro syringe pump, keeps temperature 10h, obtains orthotropic TiO at the microchannel inner surface
2/ ZnO nano-rod array.Orthotropic TiO on the microchannel inner surface that Fig. 4 obtains for this example
2The field emission scanning electron microscope photo of/ZnO nano-rod array is compared TiO with pure ZnO nanorod
2The nanorod surfaces that coats becomes very coarse and diameter also obviously becomes large.
Embodiment 4
Preparation washing lotion I (V
The concentrated sulfuric acid: V
Hydrogen peroxide: V
Distilled water=4: 1: 20) and washing lotion II (V
Ammoniacal liquor: V
Hydrogen peroxide: V
Distilled water=1: 4: 20).The microchannel is soaked among the washing lotion I at 130 ℃ of lower 30min, behind the deionized water rinsing, again the microchannel is soaked among the washing lotion II at 80 ℃ of lower 30min of immersion, behind the last deionized water rinsing, dry for standby.The Zinc diacetate dihydrate ethanolic solution of preparation 0.005M, the NaOH ethanolic solution of 0.02M, the zinc nitrate hexahydrate solution of 2M, the hexa solution of 2M.Zinc diacetate dihydrate ethanolic solution and NaOH ethanolic solution are sucked respectively the syringe of two 10mL, it is 5 μ L/min that the setting micro syringe pump pushes away speed, it is transported to the microchannel that places in advance 60 ℃ of baking ovens simultaneously, stop to carry after filling with the microchannel, behind the reaction 1.5h oven temperature is increased to 150 ℃ of annealing, time 1.5h.Successively utilize ethanol, washed with de-ionized water microchannel, and 150 ℃ of lower oven dry, obtain ZnO crystal seed layer film at the microchannel inner surface.Utilize subsequently micro syringe pump that zinc nitrate hexahydrate solution and hexa solution are transported in the microchannel of existing ZnO crystal seed simultaneously, after reacting 1.5h under 90 ℃ in the baking oven, stop delivered solution, clean the microchannel and at 150 ℃ of lower oven dry 1h, obtain orthotropic ZnO nano-rod array at the microchannel inner surface.At last with the TiO of 3mg/mL
2Colloidal sol is filled with the microchannel 4 times that the length that places 80 ℃ of baking ovens has ZnO nanorod with micro syringe pump, keeps temperature 12h, obtains orthotropic TiO at the microchannel inner surface
2/ ZnO nano-rod array.Orthotropic TiO on the microchannel inner surface that Fig. 5 obtains for this example
2The field emission scanning electron microscope photo of/ZnO nano-rod array is compared with pure ZnO nanorod, and the nanorod surfaces space coarse and that diameter also obviously becomes between the large and original ZnO nanorod that becomes diminishes greatly.
Claims (3)
1. micro-channel vertical-growth TiO
2The preparation method of clading ZnO nano rod array comprises:
(1) cleaning of microchannel with capillary glass tube as the microchannel, the microchannel is soaked in the washing lotion I at 110～130 ℃ of lower 10～30min, behind the deionized water rinsing, again the microchannel is soaked in the washing lotion II in 60～80 ℃ of lower immersion 10～30min, also oven dry behind the last deionized water rinsing; Wherein, washing lotion I component is the concentrated sulfuric acid, hydrogen peroxide and distilled water, and its volume ratio satisfies V
The concentrated sulfuric acid: V
Hydrogen peroxide: V
Distilled water=4:1:20, washing lotion II component is ammoniacal liquor, hydrogen peroxide and distilled water, its volume ratio satisfies V
Ammoniacal liquor: V
Hydrogen peroxide: V
Distilled water=1:4:20;
(2) ZnO crystal seed layer thin film technology on the inner surface of microchannel
The alcoholic solution of preparation 0.001～0.01M zinc salt, 0.004～0.04M alkali alcosol, two solution suck respectively the syringe of two 10mL, it is 5～50 μ L/min that the setting micro syringe pump pushes away speed, two solution are transported to simultaneously the microchannel that places in advance 30～80 ℃ of baking ovens, fluid stops to carry after filling with the microchannel, oven temperature is increased to 150～200 ℃ of annealing, time 1～2h, successively utilize absolute ethyl alcohol, washed with de-ionized water microchannel, and at 150～160 ℃ of lower oven dry 1～2h, obtain ZnO crystal seed layer film at the microchannel inner surface; Wherein, alkali is alkali metal hydroxide, ammoniacal liquor, urea or hydrazine hydrate;
(3) preparation of orthotropic ZnO nano-rod array on the inner surface of microchannel
The zinc solution of preparation 0.025～2M, 0.025 the amine aqueous solution of～2M, two solution suck respectively the syringe of two 10mL, it is 5～50 μ L/min that the setting micro syringe pump pushes away speed, two solution are transported in the microchannel that is shaped with in advance the ZnO crystal seed simultaneously, behind 85～120 ℃ of lower reaction 60～120min, stop delivered solution in the baking oven, with the washed with de-ionized water microchannel and at 150～200 ℃ of lower oven dry 1～2h, obtain orthotropic ZnO nano-rod array at the microchannel inner surface; Wherein, the zinc salt in step (2) and (3) is zinc acetate, zinc sulfate, zinc chloride or zinc nitrate; Amine is hexa or diethylenetriamine;
(4) vertical-growth TiO on the inner surface of microchannel
2The preparation of clading ZnO nano rod array
Be 3～5mg/mL with concentration, pH is 3.8～4.2 TiO
2Be transported to grow in the microchannel that ZnO nano-rod array is arranged in the syringe of colloidal sol suction 10mL and with micro syringe pump and coat, after colloidal sol is full of the microchannel, stop to carry, and the microchannel is placed 80～90 ℃ of baking oven 10～12h, obtain orthotropic TiO at the microchannel inner surface
2The ZnO nano-rod array that coats.
2. by a kind of micro-channel vertical-growth TiO claimed in claim 1
2The preparation method of clading ZnO nano rod array is characterized in that: the alcohol in the described step (2) is methyl alcohol or ethanol.
3. by a kind of micro-channel vertical-growth TiO claimed in claim 1
2The preparation method of clading ZnO nano rod array is characterized in that: the TiO in the described step (4)
2The Sol-gel Coated number of times is 1～4 time.
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| CN102060263B (en) * | 2010-12-17 | 2013-03-06 | 东华大学 | Preparation of ZnO/ ZnS/ Ag nano-rod array in microchannel |
| CN102614873B (en) * | 2012-03-09 | 2014-08-13 | 东华大学 | Preparation method of Pd elementary substance coated ZnO nanorod array |
| CN102689873B (en) * | 2012-05-21 | 2015-05-13 | 东华大学 | Preparation method for orientationally growing F-doped ZnO porous film on inner surface of microchannel |
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| CN103708546B (en) * | 2014-01-08 | 2015-08-26 | 安徽工业大学 | A kind of preparation method of zinc oxide/titanium oxide composite nanorod |
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| CN111682085B (en) * | 2020-07-13 | 2022-06-07 | 闽江学院 | Gold nanoarray substrate and its composite structure with near-infrared quantum tailored luminescent material and preparation method |
| CN112777627B (en) * | 2021-01-13 | 2022-11-25 | 北京化工大学 | A kind of preparation method of nano zinc oxide and nano zinc oxide |
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