CN101774537A - Preparation method of micro-channel vertical-growth TiO2-clading ZnO nano rod array - Google Patents
Preparation method of micro-channel vertical-growth TiO2-clading ZnO nano rod array Download PDFInfo
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Abstract
The invention relates to a preparation method of micro-channel vertical-growth TiO2-clading ZnO nano rod array, which comprises the following steps: capillary glass tube is adopted as a micro-channel, and firstly the micro-channel is cleaned; alcoholic solution of 0.001 to 0.01M zinc salt is prepared, alcoholic solution of .004 to 0.04M alkali is prepared, the alcoholic solution of zinc salt and alkali is simultaneously conveyed by a micro injection pump to a micro-channel of a drying box, and a layer of ZnO crystal film is obtained on the surface of the micro-channel; then a zinc salt solution of 0.025 to 2M is prepared, ammonia solution of 0.025 to 2M is prepared, and the zinc salt solution and the ammonia solution are simultaneously conveyed into the drying box, and the vertically-grown ZnO nano rod array is prepared in the micro-channel with the inner surface being prefabricated with ZnO crystal; and finally TiO2 sol with the concentration of 2 to 5 mg/mL and the pH value of 3.8 to 4.2 is convyed into the micro-channel with the vertically-grown ZnO nano rod array, and the vertically-grown TiO2-cladding ZnO nano rod array is obtained on the inner surface of the micro-channel.
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, 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 big problem.For addressing this problem, some researchers once attempted nanocatalyst such as TiO
2Nano particle is fixed in the various loads (as fiber, Al
2O
3Substrate etc.), still but greatly reduce the solid-liquid contact area of catalyst and reactant liquor like this.Another main cause that influences conductor photocatalysis efficient in addition 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 perhaps photocatalysis performance that ZnO is stronger (J.Phys.Chem.B 105 (2001) 1033-1040), and monodimension nanometer material such as ZnO nano wire (J.Phys.Chem.C112 (2008) 8850-8855), four jiaos of ZnO nanometer rods (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, so TiO
2It will be the good photochemical catalyst with high catalytic activity that people expect that the ZnO nanometer rods 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, as high specific area, heat and quality transmission etc. fast, makes it in continuous light catalytic reaction and fields such as organic synthesis and biological medicine application prospects arranged.With TiO
2The ZnO nanometer rods 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; Secondly if separating after 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 the microchannel that can be polluted by organic matter by the photocatalysis cleaning, especially for the repeated use 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 and be used for light-catalysed rapidly, continuously microreactor, and this method process simple, expend for a short time, 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 in the washing lotion I at 110～130 ℃ of following 10～30min, behind the deionized water rinsing, again the microchannel is soaked in the washing lotion II and soaks 10～30min down, at last with also oven dry behind the deionized water rinsing at 60～80 ℃;
(2) preparation of ZnO crystal seed layer film 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 the syringe of two 10mL respectively, 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 30～80 ℃ of baking ovens in advance, 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 under 150～160 ℃, dry 1～2h, on the inner surface of microchannel, obtain ZnO crystal seed layer film;
(3) preparation of orthotropic ZnO nanometer stick 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 the syringe of two 10mL respectively, 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 on the ZnO crystal seed in advance simultaneously, in the baking oven 85～120 ℃ down behind reaction 60～120min, stop delivered solution, dry 1～2h down with the washed with de-ionized water microchannel and at 150～200 ℃, obtain orthotropic ZnO nanometer stick 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
With concentration is 3～5mg/mL, and pH is 3.8～4.2 TiO
2Colloidal sol sucks in the syringe of 10mL and is transported in the long microchannel that the ZnO nanometer stick array arranged of inner surface with micro syringe pump and coats, after treating that 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)
2Colloidal sol coats number of times and 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, on the inner surface of microchannel, obtained TiO
2Clading ZnO nano rod array has increased the specific area of microchannel inner surface greatly;
(2) be expected to be used to 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 nanometer stick 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 nanometer stick 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 nanometer stick 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 nanometer stick 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 nanometer stick 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 to the present invention is described 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 institute restricted portion 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 in the washing lotion I at 110 ℃ of following 10min, behind the deionized water rinsing, again the microchannel is soaked in the washing lotion II and soaks 10min down at 70 ℃, 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 the syringe of two 10mL respectively, it is 25 μ L/min that the setting micro syringe pump pushes away speed, it is transported to the microchannel that places 60 ℃ of baking ovens in advance 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, on the inner surface of microchannel, obtain ZnO crystal seed layer film 150 ℃ of oven dry down.Utilize micro syringe pump that zinc nitrate hexahydrate solution and hexa solution are transported in the microchannel of existing ZnO crystal seed simultaneously subsequently, after reacting 2h under 90 ℃ in the baking oven, stop delivered solution, clean the microchannel and dry 1h down, on the inner surface of microchannel, obtain orthotropic ZnO nanometer stick array at 150 ℃.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 the ZnO nanometer rods with micro syringe pump, keeps temperature 10h, obtains orthotropic TiO on the inner surface of microchannel
2/ ZnO nanometer stick array.The field emission scanning electron microscope photo of the ZnO nanometer stick array on the inner surface of microchannel that Fig. 1 obtains for present embodiment, as can be seen: ZnO nanometer stick 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 nanometer stick array is compared TiO with pure ZnO nanometer rods
2The nanorod surfaces that coats becomes coarse slightly and diameter becomes big slightly.
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 in the washing lotion I at 110 ℃ of following 30min, behind the deionized water rinsing, again the microchannel is soaked in the washing lotion II and soaks 30min down at 60 ℃, 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 the syringe of two 10mL respectively, it is 50 μ L/min that the setting micro syringe pump pushes away speed, it is transported to the microchannel that places 30 ℃ of baking ovens in advance 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, on the inner surface of microchannel, obtain ZnO crystal seed layer film 150 ℃ of oven dry down.Utilize micro syringe pump that zinc nitrate hexahydrate solution and hexa solution are transported in the microchannel of existing ZnO crystal seed simultaneously subsequently, after reacting 2h under 85 ℃ in the baking oven, stop delivered solution, clean the microchannel and dry 1.5h down, on the inner surface of microchannel, obtain orthotropic ZnO nanometer stick array at 160 ℃.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 the ZnO nanometer rods with micro syringe pump, keeps temperature 10h, obtains orthotropic TiO on the inner surface of microchannel
2/ ZnO nanometer stick array.Orthotropic TiO on the microchannel inner surface that Fig. 3 obtains for this example
2The transmission electron microscope photo of/ZnO nanometer stick array (Fig. 3 a) and high-resolution-ration transmission electric-lens photo (Fig. 3 b), has coated TiO around can seeing the ZnO nanometer rods
2Nano particle.
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 in the washing lotion I at 130 ℃ of following 10min, behind the deionized water rinsing, again the microchannel is soaked in the washing lotion II and soaks 10min down at 80 ℃, 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 the syringe of two 10mL respectively, it is 10 μ L/min that the setting micro syringe pump pushes away speed, it is transported to the microchannel that places 80 ℃ of baking ovens in advance 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, on the inner surface of microchannel, obtain ZnO crystal seed layer film 150 ℃ of oven dry down.Utilize micro syringe pump that zinc nitrate hexahydrate solution and hexa solution are transported in the microchannel of existing ZnO crystal seed simultaneously subsequently, after reacting 1h under 120 ℃ in the baking oven, stop delivered solution, clean the microchannel and dry 2h down, on the inner surface of microchannel, obtain orthotropic ZnO nanometer stick array at 150 ℃.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 the ZnO nanometer rods with micro syringe pump, keeps temperature 10h, obtains orthotropic TiO on the inner surface of microchannel
2/ ZnO nanometer stick array.Orthotropic TiO on the microchannel inner surface that Fig. 4 obtains for this example
2The field emission scanning electron microscope photo of/ZnO nanometer stick array is compared TiO with pure ZnO nanometer rods
2The nanorod surfaces that coats becomes very coarse and diameter also obviously becomes big.
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 in the washing lotion I at 130 ℃ of following 30min, behind the deionized water rinsing, again the microchannel is soaked in the washing lotion II and soaks 30min down at 80 ℃, 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 the syringe of two 10mL respectively, it is 5 μ L/min that the setting micro syringe pump pushes away speed, it is transported to the microchannel that places 60 ℃ of baking ovens in advance 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, on the inner surface of microchannel, obtain ZnO crystal seed layer film 150 ℃ of oven dry down.Utilize micro syringe pump that zinc nitrate hexahydrate solution and hexa solution are transported in the microchannel of existing ZnO crystal seed simultaneously subsequently, after reacting 1.5h under 90 ℃ in the baking oven, stop delivered solution, clean the microchannel and dry 1h down, on the inner surface of microchannel, obtain orthotropic ZnO nanometer stick array at 150 ℃.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 the ZnO nanometer rods with micro syringe pump, keeps temperature 12h, obtains orthotropic TiO on the inner surface of microchannel
2/ ZnO nanometer stick array.Orthotropic TiO on the microchannel inner surface that Fig. 5 obtains for this example
2The field emission scanning electron microscope photo of/ZnO nanometer stick array is compared with pure ZnO nanometer rods, and the nanorod surfaces space coarse and that diameter also obviously becomes between the big and original ZnO nanometer rods that becomes diminishes greatly.
Claims (7)
1. micro-channel vertical-growth TiO
2The preparation method of clading ZnO nano rod array comprises:
(1) cleaning of microchannel
, as the microchannel microchannel is soaked among the washing lotion I at 110～130 ℃ of 10～30min down with capillary glass tube, behind the deionized water rinsing, again the microchannel is soaked among the washing lotion II and soaks 10～30min down, behind the last deionized water rinsing and oven dry at 60～80 ℃;
(2) preparation of ZnO crystal seed layer film 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 the syringe of two 10mL respectively, 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 30～80 ℃ of baking ovens in advance, 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 under 150～160 ℃, dry 1～2h, on the inner surface of microchannel, obtain ZnO crystal seed layer film;
(3) preparation of orthotropic ZnO nanometer stick 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 the syringe of two 10mL respectively, 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 on the ZnO crystal seed in advance simultaneously, in the baking oven 85～120 ℃ down behind reaction 60～120min, stop delivered solution, dry 1～2h down with the washed with de-ionized water microchannel and at 150～200 ℃, on the inner surface of microchannel, obtain orthotropic ZnO nanometer stick array;
(4) vertical-growth TiO on the inner surface of microchannel
2The preparation of clading ZnO nano rod array
With concentration is 3～5mg/mL, and pH is 3.8～4.2 TiO
2Be transported to grow in the microchannel that the ZnO nanometer stick array is arranged in the syringe of colloidal sol suction 10mL and with micro syringe pump and coat, after treating that colloidal sol is full of the microchannel, stop to carry, and the microchannel is placed 80～90 ℃ of baking oven 10～12h, on the inner surface of microchannel, obtain orthotropic TiO
2The ZnO nanometer stick array that coats.
2. by the described a kind of micro-channel vertical-growth TiO of claim 1
2The preparation method of clading ZnO nano rod array is characterized in that 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.
3. by the described a kind of micro-channel vertical-growth TiO of claim 1
2The preparation method of clading ZnO nano rod array is characterized in that the zinc salt in described step (2) or the step (3) is zinc acetate, zinc sulfate, zinc chloride or zinc nitrate.
4. by the described a kind of micro-channel vertical-growth TiO of claim 1
2The preparation method of clading ZnO nano rod array is characterized in that the alkali in the described step (2) is alkali metal hydroxide, ammoniacal liquor, urea or hydrazine hydrate.
5. by the described a kind of micro-channel vertical-growth TiO of 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.
6. by the described a kind of micro-channel vertical-growth TiO of claim 1
2The preparation method of clading ZnO nano rod array is characterized in that the amine in the described step (3) is hexa or diethylenetriamine.
7. by the described a kind of micro-channel vertical-growth TiO of claim 1
2The preparation method of clading ZnO nano rod array is characterized in that the TiO in the described step (4)
2It is 1～4 time that colloidal sol coats number of times.
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| CN108489942A (en) * | 2018-02-02 | 2018-09-04 | 东华大学 | A kind of preparation method of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array |
| CN108489942B (en) * | 2018-02-02 | 2020-11-13 | 东华大学 | Preparation method of zinc oxide-sodium polyacrylate composite nanorod array in microchannel |
| CN108970601A (en) * | 2018-07-09 | 2018-12-11 | 中国科学院宁波材料技术与工程研究所 | A kind of photocatalysis coating and its preparation method and application with Zinc oxide/titanium dioxide heterojunction structure |
| CN111682085A (en) * | 2020-07-13 | 2020-09-18 | 闽江学院 | Gold nano array substrate, composite structure of gold nano array substrate and near-infrared quantum cutting luminescent material and preparation method of composite structure |
| CN111682085B (en) * | 2020-07-13 | 2022-06-07 | 闽江学院 | Gold nano array substrate, composite structure of gold nano array substrate and near-infrared quantum cutting luminescent material and preparation method of composite structure |
| CN112777627A (en) * | 2021-01-13 | 2021-05-11 | 北京化工大学 | Preparation method of nano zinc oxide and nano zinc oxide |
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