CN102380230B - Hierarchical micro-nanostructure omentum based light-operated oil-water separator and its application method - Google Patents
Hierarchical micro-nanostructure omentum based light-operated oil-water separator and its application method Download PDFInfo
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Abstract
The invention brings forward a hierarchical micro-nanostructure omentum based light-operated oil-water separator and its application method. The oil-water separator comprises an oil-water separator with the hierarchical micro-nanostructure omentum, a constant water surface device, a drainage device, a water gathering device and a light source device. The oil-water separator with the hierarchical micro-nanostructure omentum is composed of an oil-water mixed liquid gathering device and the hierarchical micro-nanostructure omentum, which is made from a pore structured fabric net substrate material with a microstructure and a nanorods array structured material layer which is perpendicular to the surface of the pore structured fabric net substrate material. The hierarchical micro-nanostructure omentum can have superhydrophobicity after dark storage and can have superhydrophilicity by ultraviolet light. The hierarchical micro-nanostructure omentum based light-operated oil-water separator is stable, highly efficient and environmentally friendly. With the application of the light-operated oil-water separator for oil-water separation control, light-operated water can penetrate through the omentum instead of oil. In addition, the light-operated oil-water separator can be repeatedly used.
Description
Technical field
The invention belongs to chemical, technical field of function materials, particularly a kind of light-operated water-oil separating device and application process thereof based on micro-nano hierarchy nethike embrane.
Background technology
Surface of solids controllable immersing is solving challenging world-famous puzzle such as antifog, anti-icing, drag reduction, automatically cleaning, greasy dirt dye moisture from etc. the aspect caused people's extensive concern, and embodied its advantage.In recent years, the response research that surface of solids wellability stimulates has to external world obtained researcher's extensive concern, as photoresponse, and electroresponse, thermal response, pH response, solvent response and photoelectric-synergetic response etc.Studies show that chemical composition and geometry are infiltrating two principal elements of control surface.Micro nano structure often is introduced into different material films and is used to strengthen infiltrating response range, particularly light responsive material, can realize super-hydrophobic and super hydrophilic reversible transition in different solid substrate upper surface wellabilities, and have good controllability.Change based on this extreme wellability, realized controlled water-permeable membrane, these water-permeable membranes futuramic little/receive and be extremely important aspect the understanding of fluid device and biological activity.
Recently, the water aspect that pollute on multi-functional surface, particularly handling oil has caused the concern of countries in the world.Based on material surface to oil and the intrinsic special surface wellability of water, Chinese invention patent CN1387932A, CN1721030A, CN101518695A and CN200910217895.3 and document Angew.Chem.Int.Ed.2004,43,2012; Nanotechnology 2007,18, and 015103; Macromol.Rapid Comm.2006,27,804; J.Mater.Chem.2007,17,4772; ACS Appl.Mater.Interfaces 2009,1,2613; ACS Appl.Mater.Interfaces 2010,2,677; Carbon 2010,48, and 2192; Phys.Chem.Chem.Phys.2011,13, reported " oily removal type " water-oil separating film in 14606 grades, but oily removal type water-oil separating film exists many deficiencies, as complicate fabrication process, the use that has the fluorochemical of cost height and contaminated environment, the oil water mixture that is not suitable for a small amount of oil in the big water gaging separates, and pollutes separate mesh or nethike embrane or the like easily in oil water separation process.Then, disclose water-oil separating nethike embrane with super oleophobic properties under water and preparation method thereof among the Chinese invention patent CN102029079A, realized " water removal type " water-oil separating film.
Though certain progress has been arranged in this respect, has realized that water-oil separating stable, the control of high efficiency outfield stimuli responsive still has great challenge.
Summary of the invention
At problems of the prior art, the present invention proposes a kind of light-operated water-oil separating device and application process thereof based on micro-nano hierarchy nethike embrane.Described light-operated water-oil separating device based on micro-nano hierarchy nethike embrane is the surface wettability variation by the micro-nano hierarchy nethike embrane of photocontrol, and then realizes the device of light-operated water-oil separating.The surface wettability variation of light-operated micro-nano hierarchy nethike embrane is meant from super-hydrophobic to super hydrophilic transformation, the micro-nano hierarchy nethike embrane for preparing can be realized super-hydrophobic through dark attitude storage, the surface of micro-nano hierarchy nethike embrane is Superhydrophilic under the UV-irradiation.Has ultra-hydrophobicity before a kind of ultraviolet lighting that on having the substrate of cavernous structure fabric web, prepares, has super water-wet behavior behind the ultraviolet lighting, and described micro-nano hierarchy nethike embrane all has the nano-structure array material of super fuel shedding quality under water under dark attitude storage back and ultraviolet lighting, have high efficiency photocontrol water-oil separating performance.The solid water-oil separating characteristic of this photocontrol water-oil separating device is to change and form under water special stabilize oil/water/compound interface institute by the hydrophilic and hydrophobic of its micro-nano hierarchy nethike embrane that has before and after the ultraviolet lighting to determine jointly, and the Superhydrophilic of this micro-nano hierarchy nethike embrane produces behind UV-irradiation, and it has under water automatically cleaning, the stable and eco-friendly characteristic to water.The present invention provides theoretical direction and technical support for promoting the device exploitation from fields such as, filtration, microreactors of photocontrol oils (containing the organic solvent immiscible with water) and moisture with application.
A kind of light-operated water-oil separating device based on micro-nano hierarchy nethike embrane that the present invention proposes comprises the oily-water seperating equipment with micro-nano hierarchy nethike embrane, constant surface installation, drainage system, water collecting device and light supply apparatus.Described oily-water seperating equipment with micro-nano hierarchy nethike embrane is made of oil water mixture liquid collector and micro-nano hierarchy nethike embrane.
Described oil water mixture liquid collector is penetrating tubulose in two ends or funnel-shaped container, and a fluid guidance port A can be set on its sidewall, and diameter is 1～10cm, apart from bottom 5～30cm, is used for derived score from the oil that obtains.Described micro-nano hierarchy nethike embrane is by solid gum or seal film and be fixed in bottom one end in the penetrating two ends of oil water mixture liquid collector, by this micro-nano hierarchy nethike embrane the bottom of oil water mixture liquid collector is sealed;
The oil water mixture liquid collector level that the bottom is fixed with micro-nano hierarchy nethike embrane places on the constant surface installation, the available iron stand that has clip is fixed the oil water mixture liquid collector, make micro-nano hierarchy nethike embrane be in constant surface installation inner bottom part central authorities, micro-nano hierarchy nethike embrane and constant water surface bottom of device are at a distance of 0～1cm.The top side mural margin of constant surface installation has a side cutout, is used to control water surface elevation, and constant surface installation is generally the uncovered cylindrical container at the end, and side cutout is in the uncovered end.The side cutout top is 1/10～1/2 of constant water surface bottom of device disc diameter apart from the horizontal direction distance (being the distance of the perpendicular plan range side cutout low side in residing and constant water surface bottom of device plane, side cutout top) of low side, and the bottom of this side cutout places the high 0～1cm in position of the micro-nano hierarchy nethike embrane of constant surface installation; This side cutout is used for making micro-nano hierarchy nethike embrane to be in water environment, the constant and high 0～1cm of the more micro-nano hierarchy nethike embrane of the water surface of the water surface; The purpose of this side cutout is to guarantee that amount of liquid and liquid level in the constant surface installation are constant, and when promptly adding water in constant surface installation, when the water surface reached the bottom of this otch, excess liquid can flow out from this side cutout automatically when continuing to add liquid.
Described constant surface installation level places drainage system inside; Drainage system is generally selected the funnel-form device.This drainage system flows out from its funnel-form device lower port after the water that flows out from constant water surface device side face otch can being compiled; Have the slit between the inwall of described constant water surface device side face otch bottom, below and drainage system, this slit is of a size of 1/10～1/3 of the external disc diameter in constant surface installation cylindrical container bottom.
Described water collecting device level is positioned at the drainage system below, be used to collect the water that drainage system flows out, and also can be provided with fluid guidance port B on the sidewall of this water collecting device, be used for derived score from the water that obtains, the diameter of fluid guidance port B is 1/10～1/2 of a water collecting device container diameter; Apart from 1～10cm place, water collecting device bottom.
Described light supply apparatus places the top of water collecting device, and its light source is a ultraviolet source, and wavelength is 200～400nm, and intensity is 1～800mW/cm
2The bottom of constant surface installation and drainage system is a transparent material, and as transparency silica glass, therefore the light that light supply apparatus can be sent shines towards micro-nano hierarchy nethike embrane direction.
Described micro-nano hierarchy nethike embrane has superhydrophobic characteristic after dark attitude storage, micro-nano hierarchy nethike embrane has super water-wet behavior under the ultraviolet lighting, and described micro-nano hierarchy nethike embrane all has super fuel shedding quality under water under dark attitude storage back and ultraviolet lighting.Described micro-nano hierarchy nethike embrane is made of with the nanometer stick array structural wood bed of material vertical with its surface the cavernous structure fabric web base material with micrometer structure, nanometer stick array structural wood bed of material vertical-growth has the cavernous structure fabric web substrate material surface of micrometer structure, the Superhydrophilic of this micro-nano hierarchy nethike embrane produces behind UV-irradiation, Superhydrophilic is that the nanometer stick array structural wood bed of material has hydrophily enhancing properties behind UV-irradiation, variation has taken place in the material surface chemical composition of the nanometer stick array structural wood bed of material after the illumination, even micron in the cavernous structure fabric web base material of micrometer structure and nanometer stick array structural wood bed of material vertical with its surface and the nanostructured hydrophily that also strengthened micro-nano hierarchy nethike embrane simultaneously is its acquisition Superhydrophilic.
The length of the nanometer rods in the described nanometer stick array structural wood bed of material is preferably 2 μ m～8 μ m between 1 μ m～10 μ m, the diameter of nanometer rods is preferably 50nm～500nm at 25nm～2 μ m; Spacing between nanometer rods and the nanometer rods is preferably 60nm～450nm between 20nm～2 μ m; The nanometer rods of the nanometer stick array structural wood bed of material is an inorganic material; Described inorganic material is selected from zinc oxide material, titania meterial or the stannic oxide materials a kind of;
Described poroid reticulated net base material with micrometer structure is stainless steel, copper, aluminium, iron or titanium fabric web etc.; Described micrometer structure aperture with poroid reticulated net base material of micrometer structure is 5 μ m～300 μ m, is preferably between 25 μ m～200 μ m;
Described solid gum is a kind of in epoxide-resin glue, polyurethane adhesive, modified phenolic adhesive or phenolic aldehyde-NBR stick etc.;
The described film that seals is a kind of in the TPO materials such as polystyrene, polytetrafluoroethylene (PTFE);
Described micro-nano hierarchy nethike embrane prepares by the following method:
(1) the fabric web base material that will have a cavernous structure of micrometer structure cleans up and is dry;
(2) spin coating thickness is the EGME solution of 0.1～1mol/L zinc acetate of 100～200nm in the fabric web substrate of the cavernous structure with micrometer structure that step (1) cleans up, 0.1 the titanium oxide sol of～1mol/L or the tin oxide sol of 0.1～1mol/L, carry out then after annealing in process selects after 1～5 hour to be cooled to room temperature, having obtained thickness is 100～200nm zinc oxide, the crystal seed layer of titanium oxide or tin oxide, annealing conditions is 350～450 ℃ when selecting the EGME solution of zinc acetate, annealing conditions is 450～550 ℃ when selecting titanium oxide sol, and annealing conditions is 400～600 ℃ when selecting tin oxide sol;
(3) the fabric web substrate that will prepare the cavernous structure with micrometer structure that scribbles crystal seed layer of gained places the mixed solution of zinc nitrate and hexamethylenetetramine, in the aqueous solution of butyl titanate or the aqueous solution of butter of tin, when the growing zinc oxide nanorod arrays structure, select the mixed solution of zinc nitrate and hexamethylenetetramine, wherein zinc nitrate and hexamethylenetetramine mol ratio are 1: 3～5: 1, zinc ion concentration is 0.01～0.5mol/L, when growth titanium oxide nanometer stick array structure, select the aqueous solution of butyl titanate, the proportioning of the aqueous solution of this butyl titanate is for to 5～60mL concentration being the water that adds 1～10mL butyl titanate and 0～60mL in 37% the HCl solution; When growth tin oxide nano rod array structure; Select the aqueous solution of butter of tin, the proportioning of the aqueous solution of this butter of tin is for being to add 0.01～1mol/L tin ion among 37% the HCl (for example can add SnCl to 1～10mL concentration
45H
2O) and the urea of 0.01～1mol/L.80～220 ℃ of following growing nano-rod array structures 4～48 hours, when growing in the mixed solution that is chosen in zinc nitrate and hexamethylenetetramine, preferably on 80～100 ℃ of following growing zinc oxide nanorod arrays structures 4～15 hours, when growing in the aqueous solution that is chosen in butyl titanate, the titanic oxide nanorod array structure of preferably under 80～220 ℃, growing 5～48 hours, when growing in the aqueous solution of selecting butter of tin, preferably descended growth tin oxide nano rod array structures 10～48 hours at 80～100 ℃, after being cooled to room temperature then, there is the fabric web substrate of the cavernous structure with micrometer structure of nanometer stick array structure to take out with long, clean up and drying with deionized water, obtaining growing in the fabric web substrate of the cavernous structure with micrometer structure has the micro-nano hierarchy nethike embrane of nanometer stick array structure.
Also contain the complexing agent monoethanolamine in the described EGME solution, the mol ratio of zinc acetate and monoethanolamine is 1: 3～3: 1; Described titanium oxide sol is a butyl titanate: acetylacetone,2,4-pentanedione: deionized water: the mol ratio of ethanol is 10: 1: 1: 10～1: 10: 1: 50; Described tin oxide sol is the ethanolic solution that contains butter of tin.
Cleaning in described step (1) and the step (3) can adopt cleaning agent (as liquid detergent), deionized water, ethanol, acetone and deionized water to carry out supersound washing in turn; Drying in described step (1) and the step (3) can be chosen under 30～80 ℃ of conditions toasted 1～10 hour.
The method based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane of using that the present invention proposes is specially: when utilizing the light-operated water-oil separating device based on micro-nano hierarchy nethike embrane of the present invention to carry out water-oil separating, earlier micro-nano hierarchy nethike embrane is carried out dark attitude storage 1～30d, temperature is 10～50 ℃, so that it obtains super-hydrophobicity in air.After micro-nano hierarchy nethike embrane obtains super-hydrophobicity, be placed in the constant surface installation.After oil water mixture joins the oil water mixture liquid collector, because micro-nano hierarchy nethike embrane has super-hydrophobicity, water bears anti-capillary and presses, can not enter its nanostructured, can not pass through micro-nano hierarchy nethike embrane, micro-nano hierarchy nethike embrane also has super fuel shedding quality under water simultaneously, and oil can not be by the nethike embrane of micro-nano hierarchy, and oil water mixture is with regard to the stable top that rests on oily-water seperating equipment like this.When light supply apparatus emission ultraviolet light carried out illumination, the ultraviolet lighting wavelength was 200～400nm, intensity of illumination 1～800mW/cm
2, light application time is 0.1～2 hour, micro-nano hierarchy nethike embrane obtains hydrophily.Water enters its nanostructured and in bond, has formed water-filled nanostructured layers, and water can freely pass through micro-nano hierarchy nethike embrane.Like this, the water of oil water mixture is fast by micro-nano hierarchy nethike embrane in the oily-water seperating equipment, Gu and between micro-nano hierarchy nethike embrane and profit, formed special oil/water/(referring to micro-nano hierarchy nethike embrane) discontinuous three phase boundary, significantly reduced the contact area of oil and water, and the water that is strapped in the nanostructured with micro-nano hierarchy nethike embrane produces repulsion to oil reservoir, thereby obtained the super fuel shedding quality of micro-nano hierarchy nethike embrane under water, oil can not freely pass through micro-nano hierarchy nethike embrane, has so just realized photocontrol water-oil separating.After the water-oil separating, from fluid guidance port A, pour out the oil that obtains separating, the water in the water collecting device poured out the water that obtains separating from fluid guidance port B separating the oil obtain in the oil water mixture liquid collector.
Oil in the described oil water mixture is specially hexadecane, pumping fluid, atoleine, dichloroethanes, gasoline, diesel oil, kerosene, benzene and homologue thereof, crude oil or animals and plants wet goods.
The invention has the advantages that:
(1) the light-operated water-oil separating device based on micro-nano hierarchy nethike embrane provided by the invention has stable, efficient, advantages of environment protection.
When (2) the application light-operated water-oil separating device based on micro-nano hierarchy nethike embrane provided by the invention carries out water-oil separating, micro-nano hierarchy nethike embrane can obtain super-hydrophobicity after dark attitude storage, when ultraviolet lighting, can obtain Superhydrophilic, and this film all has super fuel shedding quality under water through after the dark attitude storage or through ultraviolet lighting the time, so just can realize through dark attitude storage Hou Shui and all impermeable nethike embrane of oil, and when ultraviolet lighting, can realize water infiltration nethike embrane and oily impermeable nethike embrane.Simultaneously, has automatically cleaning characteristic under water based on nanometer stick array structural material layer material in the light-operated water-oil separating device of micro-nano hierarchy nethike embrane, be difficult for being dyed by greasy dirt, and stable to water, therefore should can repeat repeatedly to use based on the photocontrol water-oil separating device of micro-nano hierarchy nethike embrane.
(3) provided by the invention can large-area preparation based on the micro-nano hierarchy nethike embrane that has in the light-operated water-oil separating device of micro-nano hierarchy nethike embrane, and mechanical strength is good, has extraordinary application prospect in photocontrol water-oil separating and microreactor dewater the field.
Description of drawings
Fig. 1 is the light-operated water-oil separating device structural representation of the micro-nano hierarchy nethike embrane of the present invention's proposition;
Fig. 2 a: nanometer stick array structural wood bed of material front large-area scanning electromicroscopic photograph and partial sweep Electronic Speculum enlarged photograph with cavernous structure fabric web substrate material surface growth of micrometer structure;
Fig. 2 b: be nanometer stick array structural wood bed of material front scan Electronic Speculum enlarged photograph among Fig. 2 a;
Fig. 2 c: be nanometer stick array structural wood bed of material side ESEM enlarged photograph among Fig. 2 a;
Before Fig. 3 a. ultraviolet lighting, 10 microliters of water drop in the shape picture on micro-nano hierarchy nethike embrane surface in air;
Behind Fig. 3 b. ultraviolet lighting, drip the shape picture that can permeate micro-nano hierarchy nethike embrane in water in air;
Fig. 3 c. is the shape picture that water droplet can freely pass through micro-nano hierarchy nethike embrane when continuing to add water among Fig. 3 b;
Behind Fig. 3 d. ultraviolet lighting, 10 microlitre saxols drop in the shape picture on micro-nano hierarchy nethike embrane surface in water;
Among the figure:
1-oil water mixture liquid collector; The micro-nano hierarchy nethike embrane of 2-; The constant surface installation of 3-;
The 4-drainage system; The 5-water collecting device; The 6-light supply apparatus
7-fluid guidance port A; The 8-side cutout; 9-fluid guidance port B;
The 10-iron stand; The 11-direction of illumination;
The 201-nanometer stick array structural wood bed of material; 202-cavernous structure fabric web base material.
The specific embodiment
The present invention is further illustrated below in conjunction with drawings and Examples.
A kind of light-operated water-oil separating device that present embodiment provides based on micro-nano hierarchy nethike embrane, as shown in Figure 1, comprise oily-water seperating equipment, constant surface installation 3, drainage system 4, water collecting device 5 and light supply apparatus 6 with micro-nano hierarchy nethike embrane.Described oily-water seperating equipment with micro-nano hierarchy nethike embrane is made of oil water mixture liquid collector 1 and micro-nano hierarchy nethike embrane 2.
Described oil water mixture liquid collector 1 is the penetrating tubular containers in two ends, and a fluid guidance port A7 is set on its sidewall, and diameter is 1cm, apart from bottom 5cm.Described micro-nano hierarchy nethike embrane 2 is fixed in bottom one end in the penetrating two ends of oil water mixture liquid collector 1 by epoxide-resin glue, by this micro-nano hierarchy nethike embrane 2 bottom of oil water mixture liquid collector 1 is sealed;
Oil water mixture liquid collector 1 level that the bottom is fixed with micro-nano hierarchy nethike embrane 2 places on the constant surface installation 3, with the iron stand 10 that has clip that oil water mixture liquid collector 1 is fixing, make micro-nano hierarchy nethike embrane 2 be in constant surface installation 3 inner bottom part central authorities, micro-nano hierarchy nethike embrane 2 and constant surface installation 3 bottoms are at a distance of 0cm.The top side mural margin of constant surface installation 3 has a side cutout 8, and constant surface installation 3 is for there being the uncovered cylindrical container at the end, and side cutout 8 is in the uncovered end.Side cutout 8 tops are 1/10 of constant surface installation 3 bottom disc diameters far from the horizontal direction distance of bottom, and the bottom of this side cutout 8 is contour with the position of the micro-nano hierarchy nethike embrane 2 that places constant surface installation 3;
Described constant surface installation 3 levels place drainage system 4 inside; Drainage system 4 is the funnel-form device.Have the slit between the inwall of constant surface installation 3 side cutout 8 and drainage system 4, the minimum dimension at position, slit is 1/10 of constant surface installation 3 a cylindrical containers bottom disc diameter.
Described water collecting device 5 levels are positioned at drainage system 4 belows, are used to collect the water that drainage system 4 flows out, and the sidewall of this water collecting device 5 is provided with fluid guidance port B9, and the diameter of fluid guidance port B9 is 1/10 of water collecting device 5 container diameters; Apart from 1cm place, water collecting device 5 bottom.
Described light supply apparatus 6 places the top of water collecting device 5, and its light source is a ultraviolet source, and wavelength is 200nm, and intensity is 1mW/cm
2Direction of illumination 11 is towards micro-nano hierarchy nethike embrane 2 directions.Constant water surface bottom of device is the transparency silica glass of transparent material, and therefore the light that light supply apparatus 6 can be sent shines towards micro-nano hierarchy nethike embrane 2 directions.
Have super-hydrophobic after the described micro-nano hierarchy nethike embrane 2 dark attitude storages, has super water-wet behavior during ultraviolet lighting, micro-nano hierarchy nethike embrane 2 all has super fuel shedding quality under water under dark attitude storage back and ultraviolet lighting, shown in Fig. 2-a, Fig. 2-b and Fig. 2-c, be made of with the nanometer stick array structural wood bed of material 201 vertical with its surface the cavernous structure fabric web base material 202 with micrometer structure, the nanometer stick array structural wood bed of material 201 vertical-growths are on cavernous structure fabric web base material 202 surfaces with micrometer structure.
The length of the nanometer rods in the described nanometer stick array structural wood bed of material 201 is 1 μ m, and the diameter of nanometer rods is at 25nm; Spacing between nanometer rods and the nanometer rods is 20nm; The nanometer rods of the nanometer stick array structural wood bed of material 201 is zinc oxide materials;
Described poroid reticulated net base material 202 with micrometer structure is stainless steel; Described micrometer structure aperture with poroid reticulated net base material 202 of micrometer structure is 5 μ m.
Described micro-nano hierarchy nethike embrane is prepared by following method, specifically comprises following step:
(1) the fabric web base material that will have a cavernous structure of micrometer structure cleans up and 10 hours dryings of baking under 30 ℃ of conditions;
(2) spin coating thickness is the EGME solution of the 0.1mol/L zinc acetate of 100nm in the fabric web substrate of the cavernous structure with micrometer structure that step (1) cleans up, also contain the complexing agent monoethanolamine in the EGME solution, the mol ratio of zinc acetate and monoethanolamine is 1: 3; Carry out then after 350 ℃ of annealing in process select after 1 hour to be cooled to room temperature, having obtained thickness is 100nm zinc oxide crystal seed layer;
(3) the fabric web substrate that will prepare the cavernous structure with micrometer structure that scribbles crystal seed layer of gained places the mixed solution of zinc nitrate and hexamethylenetetramine, zinc nitrate and hexamethylenetetramine mol ratio are 1: 3, zinc ion concentration is 0.01mol/L, on 80 ℃ of following growing zinc oxide nanorod arrays structures 4 hours, after being cooled to room temperature then, there is the fabric web substrate of the cavernous structure with micrometer structure of nanometer stick array structure to take out with long, with deionized water clean up and under 30 ℃ of conditions 10 hours dryings of baking, obtain in the fabric web substrate of cavernous structure the micro-nano hierarchy nethike embrane 2 that growth has the nanometer stick array structure with micrometer structure.
The method based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane of using that present embodiment proposes is specially: when utilizing the light-operated water-oil separating device based on micro-nano hierarchy nethike embrane of the present invention to carry out water-oil separating, earlier micro-nano hierarchy nethike embrane 2 is carried out dark attitude storage 1d, temperature is 10 ℃, to obtain its super-hydrophobicity, shown in Fig. 3 a, be placed on then in the constant surface installation, after oil water mixture joins oily-water seperating equipment, because micro-nano hierarchy nethike embrane 2 has super-hydrophobicity, water bears anti-capillary and presses, can not enter its nanostructured, can not pass through micro-nano hierarchy nethike embrane 2, micro-nano hierarchy nethike embrane 2 has super fuel shedding quality under water simultaneously, and oil can not pass through micro-nano hierarchy nethike embrane 2, and oil water mixture is with regard to the stable top that rests on oily-water seperating equipment like this.When carrying out illumination with ultraviolet light, the ultraviolet lighting wavelength is 200nm, intensity of illumination 1mW/cm2, and light application time is 2 hours, micro-nano hierarchy nethike embrane 2 obtains Superhydrophilic.After micro-nano hierarchy nethike embrane 2 obtains Superhydrophilic, water enters its nanostructured and in bond, formed water-filled nanostructured layers, water can freely pass through micro-nano hierarchy nethike embrane 2, shown in Fig. 3 b, the water of oil water mixture passes through the nethike embrane of micro-nano hierarchy fast in the oily-water seperating equipment, shown in Fig. 3 c, Gu and between micro-nano hierarchy nethike embrane 2 and profit, formed special oil/water/(micro-nano hierarchy nethike embrane 2) discontinuous three phase boundary, significantly reduced the contact area of oil and water, and the water that is strapped in the nanostructured with micro-nano hierarchy nethike embrane 2 produces repulsion to oil reservoir, thereby the super fuel shedding quality of micro-nano under water hierarchy nethike embrane 2 makes oil can not freely pass through the nethike embrane of micro-nano hierarchy, as Fig. 3 d, so just realized water-oil separating.After the water-oil separating, fluid guidance port A7 opened to discharge separate the oil that obtains in the oil water mixture liquid collector 1, fluid guidance port B9 is opened in the container of discharge water gathering-device 5 and separate the water that obtains.Oil in the described oil water mixture is atoleine.
Embodiment 2:
The light-operated water-oil separating device based on micro-nano hierarchy nethike embrane that present embodiment proposes comprises oily-water seperating equipment, constant surface installation 3, drainage system 4, water collecting device 5 and light supply apparatus 6 with micro-nano hierarchy nethike embrane.Described oily-water seperating equipment with micro-nano hierarchy nethike embrane is made of oil water mixture liquid collector 1 and micro-nano hierarchy nethike embrane 2.
Described oil water mixture liquid collector 1 is the penetrating funnel-shaped containers in two ends, a fluid guidance port A7 is set on its sidewall, diameter is 10cm, apart from bottom 30cm, described micro-nano hierarchy nethike embrane 2 is fixed in bottom one end in the penetrating two ends of oil water mixture liquid collector 1 by polyurethane adhesive, by this micro-nano hierarchy nethike embrane 2 bottom of oil water mixture liquid collector 1 is sealed;
The oil water mixture liquid collector 1 that the bottom is fixed with micro-nano hierarchy nethike embrane places on the constant surface installation 3, with the iron stand that contains clip etc. that oil water mixture liquid collector 1 is fixing, make micro-nano hierarchy nethike embrane 2 be in constant surface installation 3 inner bottom part central authorities, micro-nano hierarchy nethike embrane 2 and constant surface installation 3 bottoms are at a distance of 1cm.The top side mural margin of constant surface installation 3 has a side cutout 8, and constant surface installation 3 is the uncovered cylindrical container, and side cutout 8 is in the uncovered end.Side cutout 8 tops are 1/2 of constant surface installation 3 bottom disc diameters far from the horizontal direction distance of bottom, and the bottom of this side cutout 8 places the isometry position of the micro-nano hierarchy nethike embrane 2 of constant surface installation 3;
Described constant surface installation 3 places drainage system 4 inside; Drainage system 4 is the funnel-form device.Have the slit between the inwall of described constant surface installation 3 side cutout bottoms, 8 below and drainage system 4, gap size is 1/3 of constant surface installation 3 a cylindrical containers bottom disc diameter.
Described water collecting device 5 is positioned at drainage system 4 belows, be used to collect the water that drainage system 4 flows out, and also be provided with fluid guidance port B9 on the sidewall of this water collecting device 5, be used for derived score from the water that obtains, the diameter of fluid guidance port B9 is 1/2 of water collecting device 5 container diameters; Apart from 10cm place, water collecting device 5 bottom.
Described light supply apparatus 6 places the top of water collecting device 5, and its light source is a ultraviolet source, and wavelength is 400nm, and intensity is 800mW/cm
2The bottom of constant surface installation 3 and drainage system 4 is the transparent material transparency silica glass, and therefore the light that light supply apparatus 6 can be sent shines towards micro-nano hierarchy nethike embrane 2 directions.
Have super-hydrophobic after the described micro-nano hierarchy nethike embrane 2 dark attitude storages, has super water-wet behavior during ultraviolet lighting, micro-nano hierarchy nethike embrane 2 all has super fuel shedding quality under water under dark attitude storage back and ultraviolet lighting, be made of with the nanometer stick array structural wood bed of material 201 vertical with its surface the cavernous structure fabric web base material 202 with micrometer structure, the nanometer stick array structural wood bed of material 201 vertical-growths are on cavernous structure fabric web base material 202 surfaces with micrometer structure.
The length of the nanometer rods in the described nanometer stick array structural wood bed of material 201 is 10 μ m, and the diameter of nanometer rods is at 25nm; Spacing between nanometer rods and the nanometer rods is at 20nm; The nanometer rods of the nanometer stick array structural wood bed of material 201 is zinc oxide materials; Described poroid reticulated net base material with micrometer structure is a copper mesh; Described micrometer structure aperture with poroid reticulated net base material of micrometer structure is 300 μ m;
Described micro-nano hierarchy nethike embrane is prepared by following method, specifically comprises following step:
(1) the fabric web base material that will have a cavernous structure of micrometer structure cleans up and 1 hour drying of baking under 80 ℃ of conditions;
(2) spin coating thickness is the EGME solution of the 1mol/L zinc acetate of 200nm in the fabric web substrate of the cavernous structure with micrometer structure that step (1) cleans up, also contain the complexing agent monoethanolamine in this EGME solution, the mol ratio of zinc acetate and monoethanolamine is 3: 1; Carry out then after 450 ℃ of annealing in process select after 5 hours to be cooled to room temperature, having obtained thickness is 200nm zinc oxide crystal seed layer, and annealing conditions is 350～450 ℃ when selecting the EGME solution of zinc acetate;
(3) the fabric web substrate that will prepare the cavernous structure with micrometer structure that scribbles crystal seed layer of gained places the mixed solution of zinc nitrate and hexamethylenetetramine, wherein zinc nitrate and hexamethylenetetramine mol ratio are 5: 1, zinc ion concentration is 0.5mol/L, 100 ℃ of following growing zinc oxide nanorod arrays structures 15 hours, after being cooled to room temperature then, there is the fabric web substrate of the cavernous structure with micrometer structure of nanometer stick array structure to take out with long, with deionized water clean up and under 80 ℃ of conditions 1 hour drying of baking, obtain in the fabric web substrate of cavernous structure the micro-nano hierarchy nethike embrane 2 that growth has the nanometer stick array structure with micrometer structure.
The method based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane of using that present embodiment proposes is specially: when utilizing the photocontrol water-oil separating device based on micro-nano hierarchy nethike embrane 2 of the present invention to carry out water-oil separating, earlier micro-nano hierarchy nethike embrane 2 is carried out dark attitude storage 30d, temperature is 50 ℃, so that it obtains super-hydrophobicity in air.After micro-nano hierarchy nethike embrane 2 obtains super-hydrophobicity, be placed in the constant surface installation 3.After oil water mixture joins oily-water seperating equipment, because micro-nano hierarchy nethike embrane 2 has super-hydrophobicity, water bears anti-capillary and presses, can not enter its nanostructured, can not pass through micro-nano hierarchy nethike embrane 2, micro-nano hierarchy nethike embrane 2 has super fuel shedding quality under water simultaneously, and oil can not pass through micro-nano hierarchy nethike embrane 2, and oil water mixture is with regard to the stable top that rests on oil water mixture liquid collector 1 like this.When light supply apparatus 6 emission ultraviolet lights carried out illumination, the ultraviolet lighting wavelength was 400nm, intensity of illumination 800mW/cm
2, light application time is 0.1 hour, micro-nano hierarchy nethike embrane 1 obtains hydrophily.Water enters its nanostructured and in bond, has formed water-filled nanostructured layers, and water can freely pass through micro-nano hierarchy nethike embrane 2.Like this, the water of oil water mixture is fast by micro-nano hierarchy nethike embrane 2 in the oily-water seperating equipment, Gu and between micro-nano hierarchy nethike embrane 2 and profit, formed special oil/water/(referring to micro-nano hierarchy nethike embrane) discontinuous three phase boundary, significantly reduced the contact area of oil and water, and the water that is strapped in the nanostructured with micro-nano hierarchy nethike embrane 2 produces repulsion to oil reservoir, thereby obtained the super fuel shedding quality of micro-nano hierarchy nethike embrane 2 under water, oil can not freely pass through micro-nano hierarchy nethike embrane 2, has so just realized photocontrol water-oil separating.After the water-oil separating, from fluid guidance port A, pour out the oil that obtains separating, the water in the water collecting device 5 poured out the water that obtains separating from fluid guidance port B9 separating the oil obtain in the oil water mixture liquid collector 1.Oil in the described oil water mixture is specially hexadecane.
Embodiment 3:
The light-operated water-oil separating device based on micro-nano hierarchy nethike embrane that present embodiment proposes comprises oily-water seperating equipment, constant surface installation 3, drainage system 4, water collecting device 5 and light supply apparatus with micro-nano hierarchy nethike embrane.Described oily-water seperating equipment with micro-nano hierarchy nethike embrane is made of oil water mixture liquid collector 1 and micro-nano hierarchy nethike embrane 2.
Described oil water mixture liquid collector 1 is the penetrating tubular containers in two ends, and a fluid guidance port A7 can be set on its sidewall, and diameter is 5cm, apart from bottom 15cm, is used for derived score from the oil that obtains.Described micro-nano hierarchy nethike embrane 2 seals film by polystyrene and is fixed in bottom in the penetrating two ends of oil water mixture liquid collector 1, by this micro-nano hierarchy nethike embrane 2 bottom of oil water mixture liquid collector 1 is sealed;
The oil water mixture liquid collector 1 that the bottom is fixed with micro-nano hierarchy nethike embrane 2 places on the constant surface installation 3, the available iron stand that contains clip etc. is fixed, make micro-nano hierarchy nethike embrane 2 be in constant surface installation 3 inner bottom part central authorities, micro-nano hierarchy nethike embrane 2 and constant water surface bottom of device are at a distance of 0.5m.The top side mural margin of constant surface installation has a side cutout 8, is used to control water surface elevation, and constant surface installation is the uncovered cylindrical container, and side cutout 8 is in the uncovered end.Side cutout 8 tops are 1/5 of constant water surface bottom of device disc diameter apart from the horizontal direction distance of low side, and the low side of this side cutout 8 places the high 0.5cm in position of the micro-nano hierarchy nethike embrane 2 of constant surface installation 3; This side cutout 8 is used for making micro-nano hierarchy nethike embrane 2 to be in water environment, the constant and more micro-nano hierarchy nethike embrane 2 high 0.5cm of the water surface of the water surface.Described constant surface installation 3 places drainage system 4 inside; Drainage system 4 is selected the funnel-form device.Have the slit between the inwall of described constant surface installation 3 side cutout 8 and drainage system 4, gap size is 1/5 of constant surface installation 3 a cylindrical containers bottom disc diameter.
Described water collecting device 5 is positioned at drainage system 4 belows, is used to collect the water that drainage system 4 flows out, and the sidewall of this water collecting device 5 is provided with fluid guidance port B9, and the diameter of fluid guidance port B9 is 1/10～1/2 of water collecting device 5 container diameters; Apart from 5cm place, water collecting device 5 bottom.
Described light supply apparatus 6 places the top of water collecting device 5, and its light source is a ultraviolet source, and wavelength is 300nm, and intensity is 500mW/cm
2).Constant surface installation 3 and drainage system 4 bottoms are the transparent material transparency silica glass, and therefore the direction of illumination 11 of the light that light supply apparatus can be sent shines towards micro-nano hierarchy nethike embrane 2 directions.
Have super-hydrophobic after the described micro-nano hierarchy nethike embrane 2 dark attitude storages, has super water-wet behavior during ultraviolet lighting, micro-nano hierarchy nethike embrane all has super fuel shedding quality under water under dark attitude storage back and ultraviolet lighting, be made of with the nanometer stick array structural wood bed of material 201 vertical with its surface the cavernous structure fabric web base material 202 with micrometer structure, the nanometer stick array structural wood bed of material 201 vertical-growths are on cavernous structure fabric web base material 202 surfaces with micrometer structure.
The length of the nanometer rods in the described nanometer stick array structural wood bed of material 201 is 2 μ m, and the diameter of nanometer rods is 50nm; Spacing between nanometer rods and the nanometer rods is 60nm; The nanometer rods of the nanometer stick array structural wood bed of material 201 is titania meterials; Described poroid reticulated net base material with micrometer structure is the aluminium net; Described micrometer structure aperture with poroid reticulated net base material of micrometer structure is 25 μ m;
Described micro-nano hierarchy nethike embrane is prepared by following method, specifically comprises following step:
(1) the fabric web base material that will have a cavernous structure of micrometer structure cleans up and is dry;
(2) spin coating thickness is the titanium oxide sol of the 0.1mol/L of 120nm in the fabric web substrate of the cavernous structure with micrometer structure that step (1) cleans up, and this titanium oxide sol is a butyl titanate: acetylacetone,2,4-pentanedione: deionized water: the mol ratio of ethanol is 10: 1: 1: 10; Carry out then after 450 ℃ of annealing in process select after 2 hours to be cooled to room temperature, having obtained thickness is 120nm titanium oxide crystal seed layer;
(3) the fabric web substrate that will prepare the cavernous structure with micrometer structure that scribbles crystal seed layer of gained places the aqueous solution of butyl titanate, and the proportioning of the aqueous solution of this butyl titanate is for being to add the 10mL butyl titanate among 37% the HCl to 5mL concentration; Growth titanic oxide nanorod array structure is 5 hours under 80 ℃, after being cooled to room temperature then, there is the fabric web substrate of the cavernous structure with micrometer structure of nanometer stick array structure to take out with long, clean up and drying with deionized water, obtaining growing in the fabric web substrate of the cavernous structure with micrometer structure has the micro-nano hierarchy nethike embrane 2 of nanometer stick array structure.
Cleaning in described step (1) and the step (3) adopts liquid detergent, deionized water, ethanol, acetone and deionized water to carry out supersound washing in turn; Drying in described step (1) and the step (3) can be chosen under 50 ℃ of conditions and toast 5 hours.
The method based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane 2 of using that present embodiment proposes is specially:
When utilizing the light-operated water-oil separating device based on micro-nano hierarchy nethike embrane of the present invention to carry out water-oil separating, earlier micro-nano hierarchy nethike embrane 2 is carried out dark attitude storage 15d, temperature is 30 ℃, so that it obtains super-hydrophobicity in air.After micro-nano hierarchy nethike embrane 2 obtains super-hydrophobicity, be placed in the constant surface installation 3.After oil water mixture joins oil water mixture liquid collector 1, because micro-nano hierarchy nethike embrane 2 has super-hydrophobicity, water bears anti-capillary and presses, can not enter its nanostructured, can not pass through micro-nano hierarchy nethike embrane 2, have simultaneously and also have super fuel shedding quality under water, oil can not pass through micro-nano hierarchy nethike embrane 2, and oil water mixture is with regard to the stable top that rests on oil water mixture liquid collector 1 like this.When light supply apparatus 6 emission ultraviolet lights carried out illumination, the ultraviolet lighting wavelength was 300nm, intensity of illumination 500mW/cm
2, light application time is 1 hour, micro-nano hierarchy nethike embrane 2 obtains hydrophily.Water enters its nanostructured and in bond, has formed water-filled nanostructured layers, and water can freely pass through micro-nano hierarchy nethike embrane 2.Like this, the water of oil water mixture is fast by micro-nano hierarchy nethike embrane 2 in the oily-water seperating equipment 1, Gu and between micro-nano hierarchy nethike embrane 2 and profit, formed special oil/water/(referring to micro-nano hierarchy nethike embrane) discontinuous three phase boundary, significantly reduced the contact area of oil and water, and the water that is strapped in the nanostructured with micro-nano hierarchy nethike embrane 2 produces repulsion to oil reservoir, thereby obtained the super fuel shedding quality of micro-nano hierarchy nethike embrane 2 under water, oil can not freely pass through micro-nano hierarchy nethike embrane 2, has so just realized photocontrol water-oil separating.After the water-oil separating, from fluid guidance port A7, pour out the oil that obtains separating, the water in the water collecting device 5 poured out the water that obtains separating from fluid guidance port B9 separating the oil obtain in the oil water mixture liquid collector 1.Oil in the described oil water mixture is pumping fluid.
Embodiment 4:
Composition, result and annexation and the embodiment 1 of present embodiment proposes a kind of light-operated water-oil separating device based on micro-nano hierarchy nethike embrane are identical, difference only is: the length of the nanometer rods in the nanometer stick array structural wood bed of material 201 of micro-nano hierarchy nethike embrane 2 is 8 μ m, and the diameter of nanometer rods is being 500nm; Spacing between nanometer rods and the nanometer rods is 450nm; The nanometer rods of the nanometer stick array structural wood bed of material 201 is titania meterials, and the poroid reticulated net base material with micrometer structure is the iron net; Micrometer structure aperture with poroid reticulated net base material of micrometer structure is 200 μ m;
Described micro-nano hierarchy nethike embrane is prepared by following method, specifically comprises following step:
(1) the fabric web base material that will have a cavernous structure of micrometer structure cleans up and is dry;
(2) spin coating thickness is the titanium oxide sol of the 1mol/L of 150nm in the fabric web substrate of the cavernous structure with micrometer structure that step (1) cleans up, carry out then after 450 ℃ of annealing in process select after 5 hours to be cooled to room temperature, having obtained thickness is 150nm titanium oxide crystal seed layer; Described titanium oxide sol is a butyl titanate: acetylacetone,2,4-pentanedione: deionized water: the mol ratio of ethanol is 1: 10: 1: 50;
(3) the fabric web substrate that will prepare the cavernous structure with micrometer structure that scribbles crystal seed layer of gained places the aqueous solution of butyl titanate, and the proportioning of the aqueous solution of this butyl titanate is for to 60mL concentration being the water that adds 1mL butyl titanate and 60mL among 37% the HCl; Growth titanic oxide nanorod array structure is 48 hours under 220 ℃, after being cooled to room temperature then, there is the fabric web substrate of the cavernous structure with micrometer structure of nanometer stick array structure to take out with long, clean up and drying with deionized water, obtaining growing in the fabric web substrate of the cavernous structure with micrometer structure has the micro-nano hierarchy nethike embrane 2 of nanometer stick array structure.
The method of a kind of light-operated water-oil separating device based on micro-nano hierarchy nethike embrane of using that present embodiment proposes and the application process of embodiment 1 are identical.
Embodiment 5:
A kind of light-operated water-oil separating device composition, result and annexation and embodiment 1 based on micro-nano hierarchy nethike embrane that present embodiment proposes is identical, difference only is: the length with the nanometer rods in the nanometer stick array structural wood bed of material 201 of micro-nano hierarchy nethike embrane is 5 μ m, and the diameter of nanometer rods is being 1 μ m; Spacing between nanometer rods and the nanometer rods is 1 μ m; The nanometer rods of the nanometer stick array structural wood bed of material 201 is stannic oxide materials, and the poroid reticulated net base material with micrometer structure is the titanium fabric web; Micrometer structure aperture with poroid reticulated net base material of micrometer structure is 100 μ m;
Described micro-nano hierarchy nethike embrane is prepared by following method, specifically comprises following step:
(1) the fabric web base material that will have a cavernous structure of micrometer structure cleans up and is dry;
(2) spin coating thickness is the tin oxide sol of the 0.1mol/L of 160nm in the fabric web substrate of the cavernous structure with micrometer structure that step (1) cleans up, carry out then after 400 ℃ of annealing in process select after 1 hour to be cooled to room temperature, having obtained thickness is the crystal seed layer of 160nm tin oxide.Tin oxide sol is the ethanolic solution that contains butter of tin;
(3) the fabric web substrate that will prepare the cavernous structure with micrometer structure that scribbles crystal seed layer of gained places the aqueous solution of butter of tin, the proportioning of the aqueous solution of this butter of tin is for to 1mL concentration being the urea that adds 1mol/L tin ion and 0.01mol/L among 37% the HCl, growth tin oxide nano rod array structure is 10 hours under 80 ℃, after being cooled to room temperature then, there is the fabric web substrate of the cavernous structure with micrometer structure of nanometer stick array structure to take out with long, clean up and drying with deionized water, obtaining growing in the fabric web substrate of the cavernous structure with micrometer structure has the micro-nano hierarchy nethike embrane 2 of nanometer stick array structure.
The method based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane of using that present embodiment proposes is identical with the application process of embodiment 1, and the oil of distinguishing in the oil water mixture that only is to be adopted is dichloroethanes.
Embodiment 6:
Composition, result and annexation and embodiment 1 based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane that present embodiment proposes are identical, difference only is: the length of the nanometer rods in the nanometer stick array structural wood bed of material 201 of micro-nano hierarchy nethike embrane 2 is 7 μ m, and the diameter of nanometer rods is being 1.5 μ m; Spacing between nanometer rods and the nanometer rods is 1.5 μ m; The nanometer rods of the nanometer stick array structural wood bed of material 201 is stannic oxide materials, and the poroid reticulated net base material with micrometer structure is the titanium fabric web; Micrometer structure aperture with poroid reticulated net base material of micrometer structure is 150 μ m;
Described micro-nano hierarchy nethike embrane is prepared by following method, specifically comprises following step:
(1) the fabric web base material that will have a cavernous structure of micrometer structure cleans up and is dry;
(2) spin coating thickness is the tin oxide sol of the 1mol/L of 180nm in the fabric web substrate of the cavernous structure with micrometer structure that step (1) cleans up, carry out then after 600 ℃ of annealing in process select after 5 hours to be cooled to room temperature, having obtained thickness is the crystal seed layer of 180nm tin oxide; Described tin oxide sol is the ethanolic solution that contains butter of tin;
(3) the fabric web substrate that will prepare the cavernous structure with micrometer structure that scribbles crystal seed layer of gained places the aqueous solution of butter of tin, the proportioning of the aqueous solution of this butter of tin is for to 10mL concentration being the urea that adds 1mol/L tin ion and 1mol/L among 37% the HCl, growth tin oxide nano rod array structure is 48 hours under 100 ℃, after being cooled to room temperature then, there is the fabric web substrate of the cavernous structure with micrometer structure of nanometer stick array structure to take out with long, clean up and drying with deionized water, obtaining growing in the fabric web substrate of the cavernous structure with micrometer structure has the micro-nano hierarchy nethike embrane 2 of nanometer stick array structure.
The method based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane of using that present embodiment proposes is identical with the application process of embodiment 1, distinguishes and only is that the oil in the oil water mixture is diesel oil.
Embodiment 7:
Light-operated water-oil separating device composition, result and annexation and embodiment 1 based on micro-nano hierarchy nethike embrane that present embodiment proposes are identical, difference only is: the length of the nanometer rods in the nanometer stick array structural wood bed of material 201 of micro-nano hierarchy nethike embrane 2 is 2 μ m, and the diameter of nanometer rods is being 2 μ m; Spacing between nanometer rods and the nanometer rods is 220nm; The nanometer rods of the nanometer stick array structural wood bed of material 201 is zinc oxide materials, and the poroid reticulated net base material with micrometer structure is the iron fabric web; Micrometer structure aperture with poroid reticulated net base material of micrometer structure is 25 μ m;
The concrete preparation process of described micro-nano hierarchy nethike embrane is as follows:
(1) the fabric web base material that will have the cavernous structure of micrometer structure passes through cleaning agent respectively, deionized water, and ethanol, acetone and deionized water carry out supersound washing, and 30 ℃ were toasted 10 hours then;
(2) the EGME solution of the 0.1mol/L zinc acetate of spin coating 100nm in the fabric web substrate of the cavernous structure that step (1) cleans up with micrometer structure, also contain the complexing agent monoethanolamine in the EGME solution, the mol ratio of zinc acetate and monoethanolamine is 3: 1,350 ℃ of annealing 5 hours, having obtained thickness was the crystal seed layer of 100nm zinc oxide then;
(3) to place zinc nitrate and hexamethylenetetramine mol ratio be 1: 3 mixed solution in the fabric web substrate of the cavernous structure with micrometer structure that will prepare the crystal seed layer that scribbles zinc oxide of gained, zinc ion concentration was 0.02mol/L, on 80 ℃ of following growing zinc oxide nanorod arrays structures 4 hours; After being cooled to room temperature, there is the fabric web substrate of the cavernous structure with micrometer structure of nanometic zinc oxide rod array structure to take out with long, rinse well with deionized water, dry, promptly obtain having micro-nano hierarchy nethike embrane 2, its front and side pattern electron scanning micrograph are shown in Fig. 2-a, Fig. 2-b and Fig. 2-c.
The method based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane of using that present embodiment proposes is specially: when utilizing the light-operated water-oil separating device based on micro-nano hierarchy nethike embrane of the present invention to carry out water-oil separating, earlier micro-nano hierarchy nethike embrane 2 is carried out dark attitude storage 1d, temperature is 10 ℃, to obtain its super-hydrophobicity, be placed on then in the constant surface installation, after oil water mixture joins oily-water seperating equipment, because micro-nano hierarchy nethike embrane 2 has super-hydrophobicity, water bears anti-capillary and presses, can not enter its nanostructured, can not pass through micro-nano hierarchy nethike embrane 2, micro-nano hierarchy nethike embrane 2 has super fuel shedding quality under water simultaneously, oil can not pass through micro-nano hierarchy nethike embrane 2, and oil water mixture is with regard to the stable top that rests on oily-water seperating equipment like this.When carrying out illumination with ultraviolet light, the ultraviolet lighting wavelength is 200nm, intensity of illumination 1mW/cm
2, light application time is 2 hours, micro-nano hierarchy nethike embrane 2 obtains Superhydrophilic.After micro-nano hierarchy nethike embrane 2 obtains Superhydrophilic, water enters its nanostructured and in bond, formed water-filled nanostructured layers, water can freely pass through micro-nano hierarchy nethike embrane 2, the water of oil water mixture is fast by micro-nano hierarchy nethike embrane 2 in the oily-water seperating equipment, Gu and between micro-nano hierarchy nethike embrane 2 and profit, formed special oil/water/(micro-nano hierarchy nethike embrane 2) discontinuous three phase boundary, significantly reduced the contact area of oil and water, and the water that is strapped in the nanostructured with micro-nano hierarchy nethike embrane 2 produces repulsion to oil reservoir, thereby the super fuel shedding quality of micro-nano under water hierarchy nethike embrane 2 makes oil can not freely pass through micro-nano hierarchy nethike embrane 2, as Fig. 3 d, so just realized water-oil separating.After the water-oil separating, fluid guidance port A7 opened to discharge separate the oil that obtains in the oil water mixture liquid collector 1, fluid guidance port B9 is opened in the container of discharge water gathering-device 5 and separate the water that obtains.Oil in the described oil water mixture is atoleine.
Embodiment 8:
Light-operated water-oil separating device composition, result and annexation based on micro-nano hierarchy nethike embrane that present embodiment proposes are identical, difference only is: the length of the nanometer rods in the nanometer stick array structural wood bed of material 201 of micro-nano hierarchy nethike embrane is 5 μ m, and the diameter of nanometer rods is being 500nm; Spacing between nanometer rods and the nanometer rods is 60nm; The nanometer rods of the nanometer stick array structural wood bed of material 201 is zinc oxide materials, and the poroid reticulated net base material with micrometer structure is the aluminium fabric web; Micrometer structure aperture with poroid reticulated net base material of micrometer structure is 200 μ m;
The concrete preparation process of described micro-nano hierarchy nethike embrane is as follows:
(1) the fabric web base material that will have the cavernous structure of micrometer structure passes through cleaning agent respectively, deionized water, and ethanol, acetone and deionized water carry out supersound washing, and 80 ℃ were toasted 1 hour then;
(2) the EGME solution of the 0.1mol/L zinc acetate of spin coating 200nm in the fabric web substrate of the cavernous structure that step (1) cleans up with micrometer structure, also contain the complexing agent monoethanolamine in the EGME solution, the mol ratio of zinc acetate and monoethanolamine is 1: 3,450 ℃ of annealing 1 hour, having obtained thickness was the crystal seed layer of 200nm zinc oxide then;
(3) to place zinc nitrate and hexamethylenetetramine mol ratio be 5: 1 mixed solution in the fabric web substrate of the cavernous structure with micrometer structure that will prepare the crystal seed layer that scribbles zinc oxide of gained, zinc ion concentration was 0.5mol/L, on 80 ℃ of following growing zinc oxide nanorod arrays structures 15 hours; After being cooled to room temperature, have the fabric web substrate of the cavernous structure with micrometer structure of nanometic zinc oxide rod array structure to take out with long, rinse well with deionized water, drying promptly obtains having micro-nano hierarchy nethike embrane 2.
The method based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane of using that present embodiment proposes is identical with the application process of embodiment 1, distinguishes and only is that the oil in the oil water mixture is kerosene.
Embodiment 9:
Present embodiment propose based on identical in composition, result and the annexation of the light-operated water-oil separating device of micro-nano hierarchy nethike embrane and the present embodiment 1, difference only is: the length with the nanometer rods in the nanometer stick array structural wood bed of material 201 of micro-nano hierarchy nethike embrane is 8 μ m, and the diameter of nanometer rods is being 50nm; Spacing between nanometer rods and the nanometer rods is 100nm; The nanometer rods of the nanometer stick array structural wood bed of material 201 is zinc oxide materials, and the poroid reticulated net base material with micrometer structure is the titanium fabric web; Micrometer structure aperture with poroid reticulated net base material of micrometer structure is 200 μ m;
The concrete preparation process of described micro-nano hierarchy nethike embrane is as follows:
(1) the fabric web base material that will have the cavernous structure of micrometer structure passes through cleaning agent respectively, deionized water, and ethanol, acetone and deionized water carry out supersound washing, and 50 ℃ were toasted 1 hour then;
(2) the 0.1mol/L titanium oxide sol of spin coating 100nm in the fabric web substrate of the cavernous structure that step (1) cleans up with micrometer structure, butyl titanate in the titanium oxide sol: acetylacetone,2,4-pentanedione: deionized water: the mol ratio of ethanol is 1: 10: 1: 50,450 ℃ of annealing 5 hours, having obtained thickness was the crystal seed layer of 100nm zinc oxide then;
(3) the fabric web substrate of the cavernous structure with micrometer structure that will prepare the crystal seed layer that scribbles zinc oxide of gained places the aqueous solution of butyl titanate, and the proportioning of the aqueous solution of this butyl titanate is for to 5mL concentration being the water that adds 10mL butyl titanate and 30mL in 37% the HCl solution; On 220 ℃ of following growing zinc oxide nanorod arrays structures 48 hours; After being cooled to room temperature, have the fabric web substrate of the cavernous structure with micrometer structure of nanometic zinc oxide rod array structure to take out with long, rinse well with deionized water, drying promptly obtains having micro-nano hierarchy nethike embrane 2.
The method based on the light-operated water-oil separating device of micro-nano hierarchy nethike embrane of using that present embodiment proposes is identical with the application process of embodiment 1, distinguishes and only is that the oil in the oil water mixture is benzene.
Claims (10)
1. the light-operated water-oil separating device based on micro-nano hierarchy nethike embrane is characterized in that: comprise the oily-water seperating equipment with micro-nano hierarchy nethike embrane, constant surface installation, drainage system, water collecting device and light supply apparatus; Described oily-water seperating equipment with micro-nano hierarchy nethike embrane is made of oil water mixture liquid collector and micro-nano hierarchy nethike embrane;
Described oil water mixture liquid collector is penetrating tubulose in two ends or funnel-shaped container, and described micro-nano hierarchy nethike embrane is by solid gum or seal the bottom that film is fixed in penetrating oil water mixture liquid collector; This micro-nano hierarchy nethike embrane has super hydrophilic and super fuel shedding quality under water, be made of with the nanometer stick array structural wood bed of material vertical with its surface the cavernous structure fabric web base material with micrometer structure, nanometer stick array structural wood bed of material vertical-growth has the cavernous structure fabric web substrate material surface of micrometer structure;
The oil water mixture liquid collector level that the bottom is fixed with micro-nano hierarchy nethike embrane places on the constant surface installation, micro-nano hierarchy nethike embrane is in constant surface installation inner bottom part central authorities, and the top side mural margin of constant surface installation has a side cutout;
Described constant surface installation level places drainage system inside, after the water that drainage system flows out constant water surface device side face otch compiles, flows out from lower port; Described water collecting device level is positioned at the drainage system below, is used to collect the water that drainage system flows out;
Described light supply apparatus places the top of water collecting device, and its light source is a ultraviolet source, and wavelength is 200～400nm, and intensity is 1～800mW/cm
2, the bottom of constant surface installation and drainage system is a transparent material, the light that light supply apparatus is sent shines towards micro-nano hierarchy nethike embrane direction.
2. a kind of light-operated water-oil separating device according to claim 1 based on micro-nano hierarchy nethike embrane, it is characterized in that: described oil water mixture liquid collector sidewall is provided with fluid guidance port A, the diameter of fluid guidance port A is 1～10cm, apart from oil water mixture liquid collector bottom 5～30cm; The sidewall of described water collecting device is provided with fluid guidance port B, and the diameter of fluid guidance port B is 1/10～1/2 of a water collecting device container diameter, apart from water collecting device bottom 1～10cm.
3. a kind of light-operated water-oil separating device according to claim 1 based on micro-nano hierarchy nethike embrane, it is characterized in that: the side cutout top of described constant surface installation is 1/10～1/2 of constant water surface bottom of device disc diameter apart from the horizontal direction distance of low side, the low side of this side cutout places the position height of the micro-nano hierarchy nethike embrane of constant surface installation, and the height that exceeds is smaller or equal to 1cm.
4. a kind of light-operated water-oil separating device according to claim 1 based on micro-nano hierarchy nethike embrane, it is characterized in that: have the slit between the inwall of described constant water surface device side face otch bottom, below and drainage system, the minimum dimension at position, slit is 1/10～1/3 of each external disc diameter in place, summit of constant surface installation cylindrical container bottom.
5. a kind of light-operated water-oil separating device according to claim 1 based on micro-nano hierarchy nethike embrane, it is characterized in that: described poroid reticulated net base material with micrometer structure is stainless steel, copper, aluminium, iron or titanium fabric web, and the micrometer structure aperture with poroid reticulated net base material of micrometer structure is 5 μ m～300 μ m; The length of the nanometer rods in the described nanometer stick array structural wood bed of material is 1 μ m～10 μ m, and the diameter of nanometer rods is 25nm～2 μ m; Spacing between nanometer rods and the nanometer rods is 20nm～2 μ m; The nanometer rods of the described nanometer stick array structural wood bed of material is an inorganic material.
6. a kind of light-operated water-oil separating device based on micro-nano hierarchy nethike embrane according to claim 5, it is characterized in that: described inorganic material is a kind of in zinc oxide material, titania meterial or the stannic oxide materials.
7. a kind of light-operated water-oil separating device according to claim 1 based on micro-nano hierarchy nethike embrane, it is characterized in that: described micro-nano hierarchy nethike embrane prepares by following step:
(1) the fabric web base material that will have a cavernous structure of micrometer structure cleans up and is dry;
(2) spin coating thickness is the EGME solution of 0.1～1mol/L zinc acetate of 100～200nm, the titanium oxide sol of 0.1～1mol/L or the tin oxide sol of 0.1～1mol/L in the fabric web substrate of the cavernous structure with micrometer structure, carry out then after annealing in process selects after 1～5 hour to be cooled to room temperature, having obtained thickness is the crystal seed layer of 100～200nm zinc oxide, titanium oxide or tin oxide;
(3) the fabric web substrate that will prepare the cavernous structure with micrometer structure that scribbles crystal seed layer of gained places the mixed solution of zinc nitrate and hexamethylenetetramine, the aqueous solution of butyl titanate or the aqueous solution of butter of tin, zinc nitrate and hexamethylenetetramine mol ratio are 1: 3～5: 1 in the mixed solution of described zinc nitrate and hexamethylenetetramine, zinc ion concentration is 0.01～0.5mol/L, and the aqueous solution proportioning of described butyl titanate is for adding the water of 1～10mL butyl titanate and 0～60mL in 5～60mL concentration is 37% HCl solution; The aqueous solution proportioning of described butter of tin is for adding the urea of 0.01～1mol/L tin ion and 0.01～1mol/L in 1～10mL concentration is 37% HCl; 80～220 ℃ of following growing nano-rod array structures 4～48 hours, after being cooled to room temperature then, there is the fabric web substrate of the cavernous structure with micrometer structure of nanometer stick array structure to take out with long, clean up and drying with deionized water, obtaining growing in the fabric web substrate of the cavernous structure with micrometer structure has the micro-nano hierarchy nethike embrane of nanometer stick array structure.
8. a kind of light-operated water-oil separating device based on micro-nano hierarchy nethike embrane according to claim 7, it is characterized in that: also contain the complexing agent monoethanolamine in the described EGME solution, the mol ratio of zinc acetate and monoethanolamine is 1: 3～3: 1.
9. a kind of light-operated water-oil separating device based on micro-nano hierarchy nethike embrane according to claim 7, it is characterized in that: described titanium oxide sol is a butyl titanate: acetylacetone,2,4-pentanedione: deionized water: the mol ratio of ethanol is 10: 1: 1: 10～1: 10: 1: 50.
10. an application rights requires the oil-water separation method of 1 described light-operated water-oil separating device based on micro-nano hierarchy nethike embrane, it is characterized in that: earlier micro-nano hierarchy nethike embrane is carried out dark attitude storage 1～30d, temperature is 10～50 ℃, so that it obtains super-hydrophobicity in air, after oil water mixture joins oily-water seperating equipment, water and oil all can not permeate nethike embrane, and when ultraviolet lighting, realization water permeates micro-nano hierarchy nethike embrane and the impermeable micro-nano hierarchy nethike embrane of oil, the ultraviolet lighting wavelength is 200～400nm, intensity of illumination 1～800mW/cm
2, light application time is 0.1～2 hour, obtains its Superhydrophilic, has formed water-filled nanostructured layers, Gu formed special oil/water/discontinuous three phase boundary between micro-nano hierarchy nethike embrane and profit, has realized light-operated water-oil separating.
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