CN101492153B - Hydrotalcite-like film with reversible change-over photoresponse soakage capability and method of producing the same - Google Patents
Hydrotalcite-like film with reversible change-over photoresponse soakage capability and method of producing the same Download PDFInfo
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- CN101492153B CN101492153B CN2009100798646A CN200910079864A CN101492153B CN 101492153 B CN101492153 B CN 101492153B CN 2009100798646 A CN2009100798646 A CN 2009100798646A CN 200910079864 A CN200910079864 A CN 200910079864A CN 101492153 B CN101492153 B CN 101492153B
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Abstract
The present invention relates to a photoresponsive wettability reversible hydrotalcite-like film and a preparation method thereof, and belongs to the technical field of hydrotalcite-like films. The chemical general expression of the film is [Zn<2+>1-xAl<3+>x(OH)2]<x+>(R)x.yH2O, wherein R represents anion of an azobenzol surfactant CF3AZO<->; and x is more than or equal to 0.2 and less than or equal to 0.4, and y is more than or equal to 0 and less than or equal to 2. The present invention has the advantages that the surface of the prepared ZnAl-R-LDHs film material has a nano/micron composite structure; the film has excellent photoresponsive wettability reversible performance; when the film is illuminated by visible light, the contact angle between the film and a water drop reaches between 145 and 159 DEG; and after the film is illuminated by ultraviolet, the contact angle between the film and the water drop reaches between 45 and 72 DEG. The method has simple process, available raw materials, low cost, and good repetitiveness; and the ZnAl-R-LDHs film grown in situ by the anion of the azobenzol surfactant can be taken as a biosensor, an intelligent film, a reversible switch device, a microfluidic device, and the like for use.
Description
Technical field
The invention belongs to the hydrotalcite film technical field, but particularly relate to hydrotalcite film of a kind of photoresponse wetting property inverse conversion and preparation method thereof, the anion intercalated hydrotalcite film of the nitrogen benzide of growth in situ on aluminium base.
Background technology
Houghite (LDHs) is also referred to as di-hydroxyl composite metal oxidate, is a kind of anionic clay, and its chemical general formula is [M
II 1-xM
III x(OH)
2]
X+(A
N-)
X/nYH
2O, wherein M
IIAnd M
IIIBe respectively divalence and trivalent metal cation, be positioned on the main body laminate; A
N-Be interlayer anion; X is M
III/ (M
II+ M
III) molar ratio; Y is the number of middle water molecule.LDHs has the adjustable sex change of laminate structure, laminate element and the interchangeability of interlayer anion.This special property that shows on chemistry and structure not only makes it have ion-exchange performance, all has in many fields such as catalysis, absorption, ion-exchange, electricity material, optical material, biosensor techniques very widely and uses.
Moistened surface is one of key character of solid surface, also is a most common class surface phenomenon, and it not only directly influences all vital movements of occurring in nature animal and plant, and also plays an important role in the mankind's daily life and industrial and agricultural production.Usually wetting property can water drops in lip-deep contact angle and weighs, and the solid surface with contact angle during less than 90 ° claims water-wetted surface, claims hydrophobic surfaces greater than 90 °.And ultra-hydrophilic surface is meant and the surface of water contact angle less than 10 °, and water droplet is sprawled rapidly fully on the surface, can not become small droplets at surface aggregation, application is widely being arranged aspect antifog and the automatically cleaning at present.For example, on the rear-view mirror of automobile, be coated with the last layer super-hydrophilic film, just can arrive antifog effect, thereby reduce traffic accident at foggy weather.Super hydrophobic surface is meant generally and the surface of water contact angle greater than 150 ° that super-hydrophobic boundary material all has boundless application prospect in industrial and agricultural production and daily life.For example, super-hydrophobic boundary material is applied on wheel barnacle and the fuel reserve tank, can reach antifouling, rot-resistant effect; Be used for the petroleum pipe line transportation and can prevent or substantially minimize the adhesion of oil, thereby reduce loss and energy consumption in the transportation at duct wall; Super-hydrophobic textiles can be made waterproof, antifouling clothes etc.In recent years, continuous development along with micro-nano science and technology, and more and more industry is to the active demand of special surface properties material, and the special infiltrating surface of control preparation has caused people's extensive concern, and super-hydrophobic and ultra-hydrophilic surface becomes the focus of research gradually.
But the boundary material of photoresponse wetting property inverse conversion is meant reversibly to change the wettability of material surface by the stimulation of ambient light, but make material surface can super-hydrophobic and super hydrophilic between inverse conversion.For example at document J.Am.Chem.Soc.2004, (126): in 62, people such as Jiang L. utilize hydrothermal method successfully to prepare array ZnO nanometer rod, have realized superhydrophobic characteristic, and the contact angle of itself and water is 150 °, and drop can tumble when surface tilt.This nanometic zinc oxide rod array film shines 2h under UV-light after, the wetting property on surface to super hydrophilic transformation, has reached 0 ° with the contact angle of water by super-hydrophobic, and drop is sprawled rapidly on this surface, and penetrates into the array material surface.After it is in the dark placed 7 days, return to super-hydrophobic state again.By illumination with in the dark place two processes alternately, realized that material is at super-hydrophobic and super reversible transition between hydrophilic.As document J.Am.Chem.Soc.2007, (129): in 4128, human sol-gel (sol-gel) methods such as Lim prepare the V of colored type
2O
5Particle ethanol aaerosol solution is coated on the silicon substrate, the V of formation
2O
5Film is in the dark placed for some time to super hydrophilic transformation by super-hydrophobic after the irradiation of UV-light, returns to super-hydrophobic state again, has reversible cycle preferably.And for example document Science 2000, (288): in 1624, people such as Ichimura then utilize the photoinduction configuration reversal of azobenzene compound to realize the infiltrating variation of photoresponse.The nitrogen benzide of transconfiguration, molecular polarity is little, is unfavorable for sprawling of water, and the cis-configuration nitrogen benzide has bigger polarity, help water the sprawling of its surface, therefore under the illumination condition of certain wavelength, cause during nitrogen benzide generation cis-trans isomerism that wetting property changes.Document Langmuir 2001, (17): in 4593, people such as Feng C. have synthesized the photoresponse polymkeric substance that a kind of side chain contains nitrogen benzide functional group, have realized the wetting property reversible transition through the photoinduction configuration reversal.Document Chem Commun.2008, in 5710, people such as Wan P. have assembled supramolecule tensio-active agent a-CD/CF3AzoSH on liquid, liquid/solid interface, under the alternately irradiated of ultraviolet and visible light, shuttle back and forth can take place in it, and realizes the infiltration character reversible transformation on surface with this.
Inorganic oxide material, as ZnO, V
2O
5Deng, by UV-light and dark alternate treatment, can make chemical environment reversible transition between oxygen room and hydroxyl of material surface, thereby realize material in super-hydrophobic and super reversible transformation between hydrophilic, but the improvement of its luminous sensitivity of chien shih has challenge when light application time of growing and dark processing.Nitrogen benzide and derivative thereof can be realized the reversible change of wetting property by the photoinduction configuration reversal, but by the unimolecular layer organic membrane cracky that adsorbs or the LB technology prepares, and the transformation amplitude is less, makes its application have certain limitation.
Summary of the invention
But the purpose of this invention is to provide hydrotalcite film of a kind of photoresponse wetting property inverse conversion and preparation method thereof.The stratiform LDHs film that provides is to utilize its nano surface/micron composite structure, and nitrogen benzide tensio-active agent negatively charged ion is carried out intercalation.Because the coarse structure of LDHs laminate makes the light responsive material that obtains have better reversible conversion performance, has strengthened hydrophobicity and wetting ability simultaneously.
But the hydrotalcite film material of light-operated wetting property inverse conversion, the chemical general formula of its rete is:
[Zn
2+ 1-xAl
3+ x(OH)
2]
x+(R)
x·yH
2O
Wherein R represents nitrogen benzide tensio-active agent negatively charged ion CF3AZO
-0.2≤x≤0.4,0≤y≤2;
This tensio-active agent anion in-situ growth zinc-aluminum gavite thin-film material (is abbreviated as: ZnAl-R-LDHs), the surface has the Nano/micron composite structure, photoresponse is carried out under the effect of configuration reversal at this composite structure and nitrogen benzide negatively charged ion, when radiation of visible light, make the contact angle of film and water droplet reach 145 °～159 °, after UV-irradiation, this film reaches 45 °～72 ° to the water droplet contact angle.
ZnAl-R-LDHs film provided by the invention is that the growth interlayer anion is NO on the aluminium base that surperficial anodic oxidation treatment is crossed
3 -, Cl
-Perhaps SO
4 2-The ZnAl-LDHs film, then by ion-exchange,, obtain the anion intercalated ZnAl-R-LDHs film of nitrogen benzide under certain condition.
Concrete preparation process is as follows:
A: purity 〉=90%, the thickness aluminium flake between 0.01～1mm is removed surface and oil contaminant with the dehydrated alcohol cleaning, with concentration is that 3～10% sodium hydroxide solution soaks the natural oxidizing layer of removing the surface, clean with deionized water again, with the aluminium flake handled as anode, as negative electrode, the sulphuric acid soln of 0.5～3mol/L is under 1～5A as ionogen at oxidation current with stereotype or stainless steel plate, electrolysis 0.5～5 hour, it is standby to obtain anodised aluminium flake;
B: with solubility divalent zinc salt Zn
2+(Y
N-)
2/n(NH
4)
nY
N-Mol ratio according to 0.05～0.5 is dissolved in and is made into mixing solutions in the deionized water, makes Zn in the mixing solutions
2+Concentration of metal ions is controlled between 0.01～0.5mol/L, is 5.5～7.5 with the pH value of weak ammonia conditioned reaction solution, obtains reaction soln; Y
N-Be NO
3 -, Cl
-, SO
4 2-In any; The preferable pH value scope of reaction soln is 6.0～7.0.
C: the aluminium flake that anodic oxidation treatment is crossed vertically is suspended in the above-mentioned reaction soln, reacts 0.5～96 hour under 25～150 ℃ of temperature.Preferable reaction conditions is 50～130 ℃ of following isothermal reactions 5～72 hours.Take out reacted aluminium base, with deionized water wash 5～6 times, nitrogen purging drying at room temperature, promptly having obtained interlayer anion is Y
N-The ZnAl-LDHs film.
D: the ZnAl-LDHs film of preparation vertically is suspended in the nitrogen benzide salt (CF3AZO that concentration is 0.01～0.1mol/L
-M
+) in the solution, in atmosphere of inert gases, in 25～60 ℃ of following isothermal reactions 2～20 hours, preferable reaction conditions is to react 5～10 hours down at 30～50 ℃, take out reacted substrate, use deionized water wash 5～6 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets the anion intercalated ZnAl-R-LDHs film of tensio-active agent.
The molecular formula of described nitrogen benzide is CF
3O-AZO-O-(CH
2)
n-COO
-M
+, wherein AZO represents the (C of nitrogen benzide functional group
6H
4-N=N-C
6H
4-), M
+Represent Na
+, K
+, n=1～11, preferable is between n=4～6.
Adopt day island proper Tianjin Rigaku D/MAX-2500VB2+/PC type X-ray diffractometer and the German Bruker Vector22 of company type Fourier transformation infrared spectrometer that sample is carried out qualitative analysis, the results are shown in Figure 1.Curve a is nitrogen benzide tensio-active agent (C among the embodiment 1 among Fig. 1
19H
18F
3N
2NaO
4, X-ray diffraction n=5) (XRD) spectrogram.Curve b is ZnAl-NO among the embodiment 1 among Fig. 1
3 -The XRD spectra of-LDHs film.Curve c is ZnAl-CF3AZO5 among the embodiment 1 among Fig. 1
--LDHs (C
19H
18F
3N
2NaO
4, the n=5) XRD spectra of film.Can show that by the XRD data LDHs that the anion intercalated back of the nitrogen benzide of n=5 forms has good crystalline structure.
With resulting ZnAl-NO among the embodiment 1
3 --LDHs film and ZnAl-CF3AZO
5 --LDHs film scrapes from aluminium base, and nitrogen benzide tensio-active agent (C
19H
18F
3N
2NaO
4, n=5) powder carries out Fourier transform infrared spectroscopy (FT-IR) respectively and characterizes, as shown in Figure 2.From Fig. 2 the c curve as can be seen, behind intercalation, the nitrogen benzide negatively charged ion is at 1386cm
-1A broad peak appears in the place, and nitrogen benzide negatively charged ion characteristic peak moves forward, and appears at 1606cm
-1With 1516cm
-1The place.In addition, the nitrogen benzide negatively charged ion is at 3441cm
-1The place the hydroxyl stretching vibration peak with at 3449cm
-1The stretching vibration peak of the laminate hydroxyl at place overlaps, and stronger hydrogen bond and other reduction effect of existence between nitrogen benzide negatively charged ion and the LDHs main body laminate is described.
Adopt Japanese HITACHI S-3500N type scanning electronic microscope (SEM) to observe the pattern in film surface and cross section thereof (all SEM samples are all handled through metal spraying).Fig. 3 a is the SEM photograph on the aluminium base surface of process anodic oxidation treatment among the embodiment 1.Fig. 3 b is the ZnAl-NO of preparation among the embodiment 1
3 -The SEM photograph of-LDHs film.By photograph as can be seen, the ab face of sexangle tabular LDHs is along having certain included angle direction growth with substrate, and by the Nano/micron composite microstructure that the side and the summit of LDHs flat board constitutes, the plane of Gou Chenging has very high roughness like this.Fig. 3 c is the ZnAl-CF3AZO5 of preparation among the embodiment 1
-The SEM photograph of-LDHs film.Compare ZnAl-CF3AZO5 with Fig. 3 b
-The laminate of-LDHs is obviously widened, and keep arranging perpendicular to the mode of substrate, and the side of the LDHs flat board behind the intercalation and summit still can constitute the Nano/micron composite structure, therefore the ZnAl-CF3AZO5 of preparation
--LDHs film has the reversible conversion performance of good photoresponse wetting property.
Adopt the German KR ü SS GmbH DSA100 of company type to drip the contact angle of conformal analysis system testing film.When the test of contact angle, each sample is averaged as last test result different place test 3 times.Testing used water droplet volume is 3 μ L.A figure is ZnAl-CF3AZO5 among Fig. 4
--LDHs film is behind radiation of visible light, and the optical photograph of water droplet on film, contact angle are 152.6 ± 2.1 °.B figure is the ZnAl-CF3AZO5 that water droplet prepares in embodiment 1 among Fig. 4
-The optical photograph of-LDHs film after UV-irradiation, its contact angle are 71.2 ± 2.1 °.As seen, because the Nano/micron composite structure of the LDHs film of growth in situ has improved ZnAl-CF3AZO5 greatly
-The wetting property of-LDHs.
The invention has the beneficial effects as follows: the ZnAl-R-LDHs thin-film material surface of preparation has the Nano/micron composite structure, has the very superior reversible conversion performance of photoresponse wetting property, under radiation of visible light, the contact angle of film and water droplet reaches 145 °～159 °, after UV-irradiation, this film reaches 45 °～72 ° to the water droplet contact angle.The used technology of this law is simple, raw material is easy to get, cost is low, good reproducibility, and the ZnAl-R-LDHs film of this nitrogen benzide tensio-active agent anion in-situ growth is expected to as biosensor, and intelligent film, invertible switch device, microfluidic device etc. obtain using.
Description of drawings
Fig. 1 is nitrogen benzide (C among the embodiment 1
19H
18F
3N
2NaO
4, n=5) tensio-active agent (a), ZnAl-NO
3 --LDHs film (b) and ZnAl-CF3AZO5
-The XRD spectra of-LDHs film (c);
Fig. 2 is the ZnAl-NO of preparation among the embodiment 1
3 -The corresponding powder (a) of-LDHs film, nitrogen benzide (C
19H
18F
3N
2NaO
4, n=5) surfactant powders (b), ZnAl-CF3AZO5
-The IR spectrogram of the corresponding powder of-LDHs film (c);
Fig. 3 is through the aluminium base surface (a) of anodic oxidation treatment, the ZnAl-NO of preparation among the embodiment 1
3 --LDHs film (b), ZnAl-CF3AZO5
-The SEM photograph of-LDHs film (c);
Fig. 4 is the reversible switching film ZnAl-CF3AZO5 of photoresponse wetting property of preparation among the embodiment 1
-After process visible light and UV-irradiation, the optical photograph of water droplet on film, contact angle are respectively 152.6 ± 2.1 ° (a), 71.2 ± 2.1 ° (b) to-LDHs respectively.
Embodiment:
Below in conjunction with embodiment the present invention further is described:
Embodiment 1:
With purity is 99.5%, and thickness is that the aluminium flake of 0.1mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks aluminium flake and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 1.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 1 hour, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.06mol Zn (NO
3)
26H
2O and 0.24mol NH
4NO
3Be dissolved in the deionized water of 600mL, the pH with the weak ammonia regulator solution is 7.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, and in 45 ℃ of following isothermal reactions 60 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO
3 --LDHs film.
The LDHs film that makes vertically is suspended in the CF3AZO5 of 0.01mol/L
-Na
+(C
19H
18F
3N
2NaO
4, n=5) in the methanol solution, react in 30 ℃, take out film after 7 hours, with deionized water wash 5～6 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-CF3AZO5
--LDHs film.
Resulting ZnAl-NO
3 --LDHs film and ZnAl-CF3AZO5
-The XRD spectra of-LDHs film is seen Fig. 1, and the FT-IR spectrogram is seen Fig. 2, and anodised aluminium base SEM photograph is seen Fig. 3 a, ZnAl-NO
3 --LDHs film SEM photograph is seen Fig. 3 b, ZnAl-CF3AZO5
--LDHs film is seen Fig. 3 c, and film is after passing through visible light and UV-irradiation respectively, and water droplet is seen Fig. 4 at the contact angle picture of film surface.Behind radiation of visible light, the contact angle of water droplet on film is 152.6 ± 2.1 °, and water droplet is changed to 71.2 ± 2.1 ° at the contact angle of film surface after UV-irradiation.
Embodiment 2:
With purity is 99.5%, and thickness is that the aluminium flake of 0.1mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks aluminium flake and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 1.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 1 hour, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.06mol Zn (NO
3)
26H
2O and 0.24mol NH
4NO
3Be dissolved in the deionized water of 600mL, the pH with the weak ammonia regulator solution is 6.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N
2In the atmosphere, in 45 ℃ of following isothermal reactions 60 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO
3 --LDHs film.
The LDHs film that makes vertically is suspended in the CF3AZO5 of 0.2mol/L
-K
+(C
19H
18F
3N
2KO
4, n=5) in the methanol solution, at N
2In the atmosphere, react in 30 ℃, take out film after 7 hours, with deionized water wash 5～6 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-CF3AZO5
--LDHs film.The film of preparation is behind radiation of visible light, and the contact angle of water droplet on film is 156.3 ± 1.2 °, and water droplet is changed to 67.5 ± 1.2 ° at the contact angle of film surface after UV-irradiation.
Embodiment 3:
With purity is 90%, and thickness is that the aluminium flake of 0.1mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks aluminium flake and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 1.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 2 hours, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.12mol Zn (NO
3)
26H
2O and 0.6mol NH
4NO
3Be dissolved in the deionized water of 600mL, the pH with the weak ammonia regulator solution is 7.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N
2In the atmosphere, in 45 ℃ of following isothermal reactions 72 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO
3 --LDHs film.
The LDHs film that makes vertically is suspended in the CF3AZO4 of 0.05mol/L
-Na
+(C
18H
14F
3N
2NaO
4, n=4) in the methanol solution, at N
2In the atmosphere, react in 30 ℃, take out film after 7 hours, with deionized water wash 5～6 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-CF3AZO4
--LDHs film.The film of preparation is behind radiation of visible light, and the contact angle of water droplet on film is 146.7 ± 2.6 °, and water droplet is changed to 62.2 ± 2.6 ° at the contact angle of film surface after UV-irradiation.
Embodiment 4:
With purity is 99.5%, and thickness is that the aluminium flake of 0.4mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 8% sodium hydroxide solution soaks the aluminium flake clock and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 1.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 2 hours, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.12mol Zn (NO
3)
26H
2O and 0.6mol NH
4NO
3Be dissolved in the deionized water of 600mL, the pH with the weak ammonia regulator solution is 7.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N
2In the atmosphere, in 45 ℃ of following isothermal reactions 72 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO
3 --LDHs film.
The LDHs film that makes vertically is suspended in the CF3AZO4 of 0.2mol/L
-K
+(C
18H
14F
3N
2KO
4, n=4) in the methanol solution, at N
2In the atmosphere, carry out ion exchange reaction in 30 ℃, take out film after 7 hours, with deionized water wash 5～6 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-CF3AZO4
--LDHs film.The film of preparation is behind radiation of visible light, and the contact angle of water droplet on film is 148.3 ± 1.8 °, and water droplet is changed to 65.1 ± 1.8 ° at the contact angle of film surface after UV-irradiation.
Embodiment 5:
With purity is 99.5%, and thickness is that the aluminium flake of 0.1mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks aluminium flake and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 3.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 1 hour, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.06mol Zn (NO
3)
26H
2O and 0.24mol NH
4NO
3Be dissolved in the deionized water of 600mL, the pH with the weak ammonia regulator solution is 6.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N
2In the atmosphere, in 75 ℃ of following isothermal reactions 36 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO
3 --LDHs film.
The LDHs film that makes vertically is suspended in the CF3AZO6 of 0.05mol/L
-Na
+(C
20H
22F
3N
2NaO
4, n=6) in the methanol solution, at N
2In the atmosphere, carry out ion exchange reaction in 60 ℃, take out film after 3 hours, with deionized water wash 5～6 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-CF3AZO6
--LDHs film.The film of preparation is behind radiation of visible light, and the contact angle of water droplet on film is 155.8 ± 3.2 °, and after UV-irradiation, water droplet is changed to 72.7 ± 3.2 ° at the contact angle of film surface.
Embodiment 6:
With purity is 80%, and thickness is that the aluminium flake of 0.4mm cleans with dehydrated alcohol and removes surface and oil contaminant, use washed with de-ionized water, is that 5% sodium hydroxide solution soaks aluminium flake and removes surperficial natural oxidizing layer with concentration, clean with deionized water at last.As anode, as negative electrode, the sulphuric acid soln of 3.0mol/L is as ionogen with stereotype with the aluminium flake handled, and oxidation current is 2A, and the reaction times is 1 hour, and it is standby to obtain anodised aluminium flake.
In the 1000mL reaction vessel, with 0.12mol Zn (NO
3)
26H
2O and 0.6mol NH
4NO
3Be dissolved in 600mL and remove CO
2Deionized water in, the pH with the weak ammonia regulator solution is 7.0 again.
Surperficial anodised aluminium base vertically is suspended in the reaction soln, at N
2In the atmosphere, in 75 ℃ of following isothermal reactions 36 hours, reaction finished the back and takes out aluminium base, rinses well with deionized water, and at room temperature the nitrogen purging drying promptly obtains ZnAl-NO
3 --LDHs film.
The LDHs film that makes vertically is suspended in the CF3AZO6 of 0.2mol/L
-K
+(C
20H
22F
3N
2KO
4, n=6) in the methanol solution, at N
2In the atmosphere, carry out ion exchange reaction in 60 ℃, take out film after 3 hours, with deionized water wash 5～6 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying promptly gets ZnAl-CF3AZO6
--LDHs film.The film of preparation is behind radiation of visible light, and the contact angle of water droplet on film is 153.7 ± 3.0 °, and water droplet is changed to 67.5 ± 3.0 ° at the contact angle of film surface after UV-irradiation.
Claims (5)
1. but the hydrotalcite film of a photoresponse wetting property inverse conversion is characterized in that, the chemical general formula of this film is: [Zn
2+ 1-xAl
3+ x(OH)
2]
X+(R)
xYH
2O, wherein R represents nitrogen benzide tensio-active agent negatively charged ion; Its molecular formula is: CF
3O-AZO-O-(CH
2)
n-COO
-, wherein AZO represents nitrogen benzide functional group :-C
6H
4-N=N-C
6H
4-, n=1～11,0.2≤x≤0.4,0≤y≤2;
This hydrotalcite film material, be abbreviated as: ZnAl-R-LDHs, the surface has the Nano/micron composite structure, photoresponse is carried out under the effect of configuration reversal at this composite structure and nitrogen benzide negatively charged ion, when radiation of visible light, make the contact angle of film and water droplet reach 145 °～159 °, after UV-irradiation, this film reaches 45 °～72 ° to the water droplet contact angle, and described ZnAl-R-LDHs film is that the growth interlayer anion is NO on the aluminium base that surperficial anodic oxidation treatment is crossed
3 -, Cl
-Perhaps SO
4 2-The ZnAl-LDHs film, then by ion-exchange, obtain the anion intercalated ZnAl-R-LDHs film of nitrogen benzide.
2. method for preparing the described hydrotalcite film of claim 1 is characterized in that preparation process is as follows:
A, purity 〉=90%, the thickness aluminium flake between 0.01～1mm cleaned with dehydrated alcohol remove surface and oil contaminant, with concentration is that 3～10% sodium hydroxide solution soaks the natural oxidizing layer of removing the surface, clean with deionized water again, with the aluminium flake handled as anode, as negative electrode, the sulphuric acid soln of 0.5～3mol/L is under 1～5A as ionogen at oxidation current with stereotype or stainless steel plate, electrolysis 0.5～5 hour, it is standby to obtain anodised aluminium flake;
B, with solubility divalent zinc salt Zn
2+(Y
N-)
2/n(NH
4)
nY
N-Mol ratio according to 0.05～0.5 is dissolved in and is made into mixing solutions in the deionized water, makes Zn in the mixing solutions
2+Concentration of metal ions is controlled between 0.01～0.5mol/L, is 5.5～7.5 with the pH value of weak ammonia conditioned reaction solution, obtains reaction soln; Y
N-Be NO
3 -, Cl
-, SO
4 2-In any;
C, the aluminium flake that anodic oxidation treatment is crossed vertically are suspended in the above-mentioned reaction soln, react 0.5～96 hour under 25～150 ℃ of temperature; Take out reacted aluminium base, with deionized water wash 5～6 times, nitrogen purging drying at room temperature, having obtained interlayer anion is Y
N-The ZnAl-LDHs film;
D, with the preparation the ZnAl-LDHs film vertically be suspended in the nitrogen benzide salts solution that concentration is 0.01～0.1mol/L, in atmosphere of inert gases, in 25～60 ℃ of following isothermal reactions 2～20 hours, take out reacted substrate, with deionized water wash 5～6 times, use the ethanol rinsing again, at room temperature the nitrogen purging drying, get the anion intercalated ZnAl-R-LDHs film of tensio-active agent, the molecular formula of described nitrogen benzide salt is CF
3O-AZO-O-(CH
2)
n-COO
-M
+, wherein AZO represents nitrogen benzide functional group :-C
6H
4-N=N-C
6H
4-, M
+Represent Na
+, K
+, n=1～11.
3. method according to claim 2 is characterized in that, the pH value scope of reaction soln is 6.0～7.0 in the B step.
4. method according to claim 2 is characterized in that, is reflected at 50～130 ℃ of following isothermal reactions 5～72 hours in the C step.
5. method according to claim 2 is characterized in that, reaction conditions is to react 5～10 hours down at 30～50 ℃ in the D step.
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