CN100406388C - Vertically oriented hydrotalcite film in nano and micron composite structure and its preparing process - Google Patents
Vertically oriented hydrotalcite film in nano and micron composite structure and its preparing process Download PDFInfo
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- CN100406388C CN100406388C CNB2005101347208A CN200510134720A CN100406388C CN 100406388 C CN100406388 C CN 100406388C CN B2005101347208 A CNB2005101347208 A CN B2005101347208A CN 200510134720 A CN200510134720 A CN 200510134720A CN 100406388 C CN100406388 C CN 100406388C
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
- B01J37/0226—Oxidation of the substrate, e.g. anodisation
Abstract
The present invention relates to vertically oriented LDHs film in nanometer and micron composite structure and its preparation process. By means of in-situ synthesis technology, and using aluminum sheet through surface anode oxidation as substrate and Al3+ source, and through dropping ammonia water to regulate the pH value of the reaction solution, reacting bivalent metal ion M2+ inside solution and ammonium nitrate in alkaline condition to produce metal complex ion to control the slow release of M2+ and the nucleation rate of LDHs on the substrate, the present invention grows oriented LDHs film with crystal face perpendicular to the substrate surface or (00l) direction and controllable density. The present invention is superior to available method, which has poor LDHs crystal orientation and other problems.
Description
Technical field:
The present invention relates to a kind of have nano and micron composite structure and vertically oriented hydrotalcite film and preparation method thereof, be specifically related to a kind of in-situ synthetic method that is grown in the hydrotalcite film on the surperficial anodised aluminum substrate.
Technical background:
Houghite, (claim layered di-hydroxyl composite metal oxidate again, be called for short LDHs) is an anionoid type laminate structure functional materials, by being parallel to each other and positively charged laminate is formed, interlayer is made of balance anion and water molecules.Its chemical constitution general formula is: [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N- X/n) mH
2O, wherein M
2+, M
3+Be respectively divalence, the trivalent metal ion that is positioned on the laminate, A
N-Represent interlayer anion.This class material is because its unique crystalline structure and physicochemical characteristic make it show very wide application prospect in many fields such as ion-exchange, absorption, catalysis, macromolecule modified, optical material, magnetics material, electricity materials.If houghite is made film,, will widen it greatly in industrial application to realize the device of multi-functional LDHs material.For example: when the catalyzer, not only can improve its service efficiency to hydrotalcite film, and can solve problems such as the separating of catalyzer and reactant, catalyst loss, recovery because of improving surface-area.When as the electrode modification material, can improve electrode performance well.
After many inorganic materials were made into the orientation film, it is functional to be strengthened to a great extent.If obtain orientation LDHs film, the above-mentioned functions of LDHs is enhanced and widens the Application Areas of such material.Yet different with other stratified material is, LDHs is difficult for making film, the orientation of its crystal grain of more difficult control in film, thereby hindered some application and developments and the device of LDHs material.At present, the preparation method of related genera hydrotalcite film also has some bibliographical informations.As document Thin SolidFilms, among the 2001:255, people such as Akihiko adopt the LB membrane technique to prepare the hybrid film of Ni-Al hydrotalcite and ruthenium containing metal title complex.Document Adv.Mater.2001,13 (16): in 1263, people such as E.Gandner are deposited on the magnalium LDHs film that has obtained the alkoxyl group intercalation on glass with the colloidal solution of LDHs.In addition, at document Chem.Mater.2004, in 16,3774, people such as Jung utilize ultransonic method that Mg-Al hydrotalcite colloidal particle is spread over monocrystalline silicon surface, and drying is handled and obtained the Mg-Al hydrotalcite film that individual layer is arranged then.Document Chem.Commun.2003:2740 and Langmuir, 1998,14 (10): in 2890, people such as J.H.Lee and K.Yao respectively with the LDHs crystal deposition in the aqueous solution on the thermo-cracking graphite and silicon (100) wafer of high orientation, though have certain orientation, LDHs is discontinuous, density is low, and not tight with matrix bond, practicality is not high.The hydrotalcite film of above method preparation all exist LDHs crystal grain arrange unordered, density is not high, with the bonding force of matrix a little less than, easily come off from matrix, defectives such as preparation method's complexity cause its range of application to be very limited.In application number was 200410090816.4 patent application, we utilized the urea low-temperature decomposition to provide OH for the hydrotalcite synthetic system
-And CO
3 2-Prepared with aluminium is the hydrotalcite-like structuring catalyst of matrix, but the Mg-Al hydrotalcite film for preparing does not have orientation, be that the neatly crystal grain orientation of arranging on matrix is at random, and required reaction times of this preparation method is longer, generally need 7 days at least, therefore be difficult to the density degree of control film.
Summary of the invention:
The purpose of this invention is to provide on a kind of aluminium flake after surperficial anodic oxidation that original position is synthetic to have nano and micron composite structure and vertically oriented hydrotalcite film and preparation method thereof, solve in the LDHs film of preparation in the past LDHs crystalline orientation difference and easily from substrate come off, problem such as matrix poor heat stability.
Provided by the invention have nano and micron composite structure and a vertical orientated hydrotalcite film, is to be grown in the LDHs film of surface on the aluminium substrate after the anodic oxidation, and the chemical general formula of rete LDHs is:
[M
2+ 1-xAl
3+ x(OH)
2]
x+(CO
3 2-)
x/2·yH
2O，
M wherein
2+Represent divalent-metal ion Mg
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any, that preferable is Ni
2+, Zn
2+Or Mg
2+0.2≤x≤0.4,0≤y≤2.
This LDHs film has nano and micron composite structure and vertical orientated ((001) crystal face is perpendicular to matrix surface), and the thickness of film is at 1～2.5 μ m.
The present invention adopts the original position synthetic technology, to be matrix through the aluminium flake after the surperficial anodic oxidation, utilizes the anodised aluminium on the substrate surface to provide the hydrotalcite growth required Al
3+The source by the pH value of dropping ammonia conditioned reaction solution, makes divalent-metal ion M in the solution
2+Under alkaline condition, generate the metal complex ion with ammonium nitrate, reach control divalent-metal ion M
2+The slow purpose that discharges, thereby the successful nucleation rate of control LDHs on matrix, it is controlled to grow density, has nano and micron composite structure and the vertical orientated hydrotalcite film that is (001) crystal face perpendicular to matrix surface.
Concrete synthesis step is as follows:
A: with purity greater than 80%, thickness is used ethanol ultrasonic cleaning 5-10min earlier at the aluminium flake of 0.01mm～1mm, and water ultrasonic cleaning 5-10min removes surface and oil contaminant again, makes anode then on anodic oxidation device, make negative electrode with stereotype or stainless steel plate, electrolytic solution is 0.5～3.0molL
-1Sulphuric acid soln, oxidation current is 1～5A, with taking out behind aluminium flake anodic oxidation 30～100min, rinses out electrolytic solution with deionized water, it is standby to obtain anodic alumina film;
B: with ammonium nitrate and solubility divalence inorganic salt M
2+Y is by 3～30: 1 mol ratio is dissolved in the deionized water, M
2+Concentration of metal ions is controlled at 0.01～0.5mol/L, and the pH value of the weak ammonia conditioned reaction solution with 1% is 4.5～10, obtains reacting synthetic liquid;
C: surperficial anodised aluminium substrate is suspended in the reaction soln, reacted 0.5～96 hour down, take out aluminium substrate at 25～180 ℃, dry under 25～90 ℃, promptly obtain houghite (LDHs) film.
M among the step B
2+Be Mg
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any, that preferable is Ni
2+, Zn
2+Or Mg
2+, Y is CO
3 2-, NO
3 -, SO
4 2-, Cl
-, F
-, Br
-In any, that preferable is CO
3 2-, NO
3 -Or Cl
-The preferable pH value scope of reaction soln is 5.5～8.5.
The preferable reaction conditions of step C is to react 3～60 hours down at 50～150 ℃, and better reaction conditions is 50～130 ℃ of reactions down, 5～20 hours.
This preparation method's characteristics are: with the anodised aluminium on the substrate surface is that the hydrotalcite growth provides Al
3+The source by the pH value of regulator solution, makes metal ion and ammonium nitrate generate the metal complex ion under alkaline condition, reaches control divalent-metal ion M
2+The slow purpose that discharges, thereby the successful nucleation rate of control LDHs on matrix, it is controlled to grow density, has the hydrotalcite film of nano and micron composite structure and vertical orientated ((001) crystal face is perpendicular to matrix surface).It is fast that this preparation method has speed of response, just can obtain the thick hydrotalcite film of 1 μ m in general 3～4 hours, time lengthening to 60 hour, and film thickness can reach 2.5 μ m.
Adopt day island proper Tianjin XRL-6000A type X-ray diffractometer (XRD) and the German Bruker Vector22 of company type Fourier transformation infrared spectrometer that sample is carried out qualitative analysis.Curve a is the XRD figure spectrum of the aluminium flake after the surface anodic oxidation of embodiment 1 steps A gained among Fig. 1, and these three peaks belong to (110) for aluminium substrate, (200), (220) diffraction peak respectively.Curve b is the XRD spectra of embodiment 1 step C gained film sample among Fig. 1, and clearly as can be seen, except three diffraction peaks of aluminium substrate, other diffraction peak can belong to (012) for LDHs, (110), (113) diffraction peak.Curve c is the XRD figure spectrum of the powder that scrapes off from embodiment 1 gained film sample among Fig. 1, finds out that obviously the diffraction peak of each crystal face of LDHs has all occurred.Curve b compares with c among Fig. 1, and (001) diffraction peak of the XRD spectra of film sample has disappeared, and the nickel aluminium carbonate LDHs film that the present invention preparation is described has vertical orientated, and promptly (001) crystal face is grown perpendicular to matrix surface.Embodiment 1 gained powdered sample is carried out Fourier transform infrared spectroscopy (FT-IR) characterize as shown in Figure 2 1355cm
-1The strong absorption peak at place can belong to and is nickel aluminium carbonate LDHs interlayer anion CO
3 2-Feature symmetrical stretching vibration absorption peak.
Adopt the pattern (for more clear all the SEM samples of photograph are all handled through metal spraying) in Japanese HITACHI S-3500N type scanning electronic microscope (SEM) and observation film surface and cross section thereof.Fig. 3 is the SEM photograph on the aluminium flake surface after the surface anodic oxidation of embodiment 1 gained, and Fig. 4 is the surperficial SEM photograph and the constituency EDS spectrogram of the film sample of embodiment 1 preparation.Fig. 5 is the section S EM photograph of the sample of embodiment 1 preparation, can be clear that by figure, have the very fine and close flaky substance of one deck on the anodised aluminium surface, i.e. (001) crystal face (or ab face) of the LDHs thin film layer of Xing Chenging, and LDHs is perpendicular to matrix surface.The thickness of this LDHs layer is at micron order.It is as follows to obtain each atoms of elements content (%) by constituency EDS spectrogram:
Calculating the Mg/Al mol ratio is 4.41.
XRD, FT-IR, SEM and EDS result show that all the anodized surface at aluminum substrate has formed fine and close LDHs thin film layer, and (001) crystal face (or ab face) of LDHs is perpendicular to matrix surface.
The present invention has following unusual effect:
By control reaction temperature and time, can obtain the different hydrotalcite film of density degree, thus the nano and micron composite structure of modulation film.The hydrotalcite film that employing a process for preparing has vertical orientated, (001) diffraction peak disappears in the XRD spectra of gained film sample, and to prove absolutely that just it has vertical orientated, be that LDHs (001) crystal face is grown perpendicular to matrix surface, and LDHs crystal grain in process of growth owing to be subjected to stress, produced crooked (see figure 4), compare with the general hydrotalcite that does not have bending, it is applied in the snappiness that can improve material in the macromolecular material as additive.
Description of drawings
Fig. 1 is the XRD figure spectrum of aluminium flake matrix, nickel aluminium carbonate LDHs film and corresponding powder after the embodiment 1 surperficial anodic oxidation;
Fig. 2 is the IR collection of illustrative plates of embodiment 1 gained nickel aluminium carbonate LDHs powder;
Fig. 3 is the SEM photograph on the aluminium flake surface after the surface anodic oxidation of embodiment 1 gained;
Fig. 4 is the SEM photograph and the constituency EDS spectrogram in embodiment 1 gained nickel aluminium carbonate LDHs film front;
Fig. 5 is the SEM photograph in embodiment 1 gained nickel aluminium carbonate LDHs film cross section;
Fig. 6 is the SEM combination photograph in embodiment 3 gained nickel aluminium carbonate LDHs film fronts, wherein Fig. 6 a is a SEM photograph of executing 6 hours gained nickel aluminium carbonate LDHs film fronts of example 3 reactions, Fig. 6 b is a SEM photograph of executing 12 hours gained nickel aluminium carbonate LDHs film fronts of example 3 reactions, Fig. 6 c is a SEM photograph of executing 18 hours gained nickel aluminium carbonate LDHs film fronts of example 3 reactions, and Fig. 6 d is a SEM photograph of executing 24 hours gained nickel aluminium carbonate LDHs film fronts of example 3 reactions;
Embodiment:
The invention will be further described below in conjunction with embodiment:
Embodiment 1:
With thickness is the ethanol ultrasonic cleaning 5min of aluminium flake elder generation of 0.1mm (purity is 99.5%), water ultrasonic cleaning 5min removes surface and oil contaminant again, and anodic oxidation 50min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is 1.0molL
-1Sulphuric acid soln, oxidation current is 2A.
In the 10L Erlenmeyer flask, with 1mol Ni (NO
3)
26H
2O and 6mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 7.5 again.
Surperficial anodised aluminium substrate is suspended in the solution, and behind the sealed vessel, isothermal reaction is 6 hours under 120 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, 40 ℃ of oven dry down, promptly obtains the LDHs film.
The XRD spectra of gained LDHs film is seen Fig. 1, and the FT-IR spectrogram is seen Fig. 2, and the SEM photograph is seen Fig. 4 and Fig. 5, shows that the aluminum substrate surface has formed nickel aluminium carbonate LDHs thin film layer.The Ni/Al mol ratio is 4.41 in the LDHs layer, and thickness is about 2.5 μ m.
Embodiment 2:
With thickness is the aluminium flake ethanol ultrasonic cleaning 10min of 0.05mm (purity is 99%), water ultrasonic cleaning 10min removes surface and oil contaminant again, and anodic oxidation 30min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is 1.0molL
-1Sulphuric acid soln, oxidation current is 2A.
In the 10L Erlenmeyer flask, with 1mol Ni (NO
3)
26H
2O and 3mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 5.5 again.
Surperficial anodised aluminium substrate is suspended in the solution, and behind the sealed vessel, isothermal reaction is 36 hours under 75 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, 40 ℃ of oven dry down, promptly obtains the LDHs film.
Gained nickel aluminium carbonate thin film layer Ni/Al mol ratio is 2.56, and thickness is about 2.3 μ m.
Embodiment 3:
Be 99.5% aluminium flake with ethanol ultrasonic cleaning 5min with 4 thickness for 0.1mm purity respectively, water ultrasonic cleaning 5min removes surface and oil contaminant again, and anodic oxidation 50min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is 1.0molL
-1Sulphuric acid soln, oxidation current is 2A.
In the 10L Erlenmeyer flask, with 1mol Ni (NO
3)
26H
2O and 3mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 7.0 again.
4 anodised aluminium substrates in surface are suspended in the solution, and behind the sealed vessel, isothermal reaction under 100 ℃ of temperature respectively at 6,12,18,24 hours taking-up a slice aluminium substrates, is rinsed well with deionized water, 40 ℃ of oven dry down, promptly obtains the LDHs film.
The SEM photograph of gained LDHs film is seen Fig. 6, wherein Fig. 6 a is the SEM photograph in 6 hours gained nickel aluminium carbonate LDHs film fronts of reaction, Fig. 6 b is the SEM photograph in 12 hours gained nickel aluminium carbonate LDHs film fronts of reaction, Fig. 6 c is the SEM photograph in 18 hours gained nickel aluminium carbonate LDHs film fronts of reaction, and Fig. 6 d is the SEM photograph in 24 hours gained nickel aluminium carbonate LDHs film fronts of reaction; From this group SEM photograph, find out that obviously the aluminum substrate surface has formed the LDHs thin layer.From react 6 hours the film photo as can be seen, the hydrotalcite film surface growth must be more sparse, prolongs the reaction times, it is more and more finer and close that hydrotalcite film becomes, and extends to 24 hours when the reaction times, hydrotalcite grows into the film of one deck densification.This picture group sheet can prove absolutely, can control the density degree of hydrotalcite film well by controlling reaction time.
Gained nickel aluminium carbonate thin film layer Ni/Al mol ratio is respectively 1.5,1.8,2.1,2.5
Embodiment 4
With thickness is the aluminium flake ethanol ultrasonic cleaning 10min of 0.05mm (purity is 99%), water ultrasonic cleaning 10min removes surface and oil contaminant again, and anodic oxidation 30min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is 2.0molL
-1Sulphuric acid soln, oxidation current is 2A.
In the 10L Erlenmeyer flask, with 1mol Zn (NO
3)
26H
2O and 8mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 8.5 again.
Surperficial anodised aluminium substrate is suspended in the solution, and behind the sealed vessel, isothermal reaction is 60 hours under 80 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, 40 ℃ of oven dry down, promptly obtains the LDHs film.
Gained nickel aluminium carbonate thin film layer Zn/Al mol ratio is 2.5, and thickness is about 1.85 μ m.
Embodiment 5:
With thickness is the aluminium flake ethanol ultrasonic cleaning 10min of 0.05mm (purity is 99%), water ultrasonic cleaning 10min removes surface and oil contaminant again, and anodic oxidation 30min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is 2.0molL
-1Sulphuric acid soln, oxidation current is 2A.
In the 10L Erlenmeyer flask, with 1mol Zn (NO
3)
26H
2O and 8mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 5.5 again.
Surperficial anodised aluminium substrate is suspended in the solution, and behind the sealed vessel, isothermal reaction is 18 hours under 60 ℃ of temperature, and question response finishes the back and takes out aluminium substrate, rinses well with deionized water, 40 ℃ of oven dry down, promptly obtains the LDHs film.
Gained nickel aluminium carbonate thin film layer Zn/Al mol ratio is 1.74, and thickness is about 1.63 μ m.
Embodiment 6:
With thickness is the aluminium flake ethanol ultrasonic cleaning 5min of 0.1mm (purity is 99.5%), water ultrasonic cleaning 5min removes surface and oil contaminant again, and anodic oxidation 50min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is 1.0molL
-1Sulphuric acid soln, oxidation current is 2A.
In the 10L Erlenmeyer flask, with 1mol Mg (NO
3)
26H
2O and 12mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 6.5 again.
Surperficial anodised aluminium substrate is suspended in the solution, and behind the sealed vessel, isothermal reaction is 21 hours under 90 ℃ of temperature.Question response finishes the back and takes out aluminium substrate, rinses well with deionized water, 40 ℃ of oven dry down, promptly obtains the LDHs film.
Gained nickel aluminium carbonate thin film layer Mg/Al mol ratio is 1.6, and thickness is about 1.56 μ m.
Embodiment 7:
With thickness is the aluminium flake ethanol ultrasonic cleaning 10min of 0.05mm (purity is 99%), water ultrasonic cleaning 10min removes surface and oil contaminant again, and anodic oxidation 30min on anodic oxidation device takes out aluminium flake then, rinse out electrolytic solution with deionized water, it is standby to obtain anodic alumina film.Anodic oxidation device adopts stereotype or stainless steel plate to make negative electrode, and electrolytic solution is 2.0molL
-1Sulphuric acid soln, oxidation current is 2A.
In the 10L Erlenmeyer flask, with 1mol Mg (NO
3)
26H
2O and 6mol NH
4NO
3Be dissolved in the deionized water, the pH with 1% weak ammonia regulator solution is 7.5 again.
Surperficial anodised aluminium substrate is suspended in the solution, and behind the sealed vessel, isothermal reaction is 35 hours under 50 ℃ of temperature.Question response finishes the back and takes out aluminium substrate, rinses well with deionized water, 40 ℃ of oven dry down, promptly obtains the LDHs film.
Gained nickel aluminium carbonate thin film layer Mg/Al mol ratio is 2.8, and thickness is about 2.37 μ m.
Claims (5)
1. a vertically oriented hydrotalcite film in nano and micron composite structure is a kind of LDHs film of surface on the aluminium substrate after the anodic oxidation that be grown in, and the chemical general formula of rete LDHs is:
[M
2+ 1-xAl
3+ x(OH)
2]
x+(CO
3 2-)
x/2·yH
2O)，
M wherein
2+Represent divalent-metal ion Mg
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any;
0.2≤x≤0.4，0≤y≤2；
This LDHs film has nano and micron composite structure and vertical orientated, and promptly (001) crystal face is perpendicular to matrix surface, and the thickness of film is at 1～2.5 μ m.
2. vertically oriented hydrotalcite film in nano and micron composite structure according to claim 1 is characterized in that: M in the chemical general formula of rete LDHs
2+Be Ni
2+, Zn
2+Or Mg
2+
3. the preparation method of a vertically oriented hydrotalcite film in nano and micron composite structure as claimed in claim 1, concrete steps are as follows:
A: with purity greater than 80%, thickness is used ethanol ultrasonic cleaning 5-10min earlier at the aluminium flake of 0.01mm～1mm, and water ultrasonic cleaning 5-10min removes surface and oil contaminant again, makes anode then on anodic oxidation device, make negative electrode with stereotype or stainless steel plate, electrolytic solution is 0.5～3.0molL
-1Sulphuric acid soln, oxidation current is 1～5A, with taking out behind aluminium flake anodic oxidation 30～100min, rinses out electrolytic solution with deionized water, it is standby to obtain anodic alumina film;
B: with ammonium nitrate and solubility divalence inorganic salt M
2+Y is by 3～30: 1 mol ratio is dissolved in the deionized water, M
2+Concentration of metal ions is controlled at 0.01～0.5mol/L, and the pH value of the weak ammonia conditioned reaction solution with 1% is 4.5～10, obtains reacting synthetic liquid; M wherein
2+Be Mg
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any, Y is CO
3 2-, NO
3 -, SO
4 2-, Cl
-, F
-, Br
-In any;
C: surperficial anodised aluminium substrate is suspended in the reaction soln, reacted 0.5～96 hour down, take out aluminium substrate at 25～180 ℃, dry under 25～90 ℃, promptly obtain hydrotalcite film.
4. according to the preparation method of the described vertically oriented hydrotalcite film in nano and micron composite structure of claim 3, it is characterized in that: M among the step B
2+Be Ni
2+, Zn
2+Or Mg
2+, Y is CO
3 2-, NO
3 -Or Cl
-The pH value scope of reaction soln is 5.5～8.5;
The reaction conditions of step C is to react 3～60 hours down at 50～150 ℃.
5. according to the preparation method of the described vertically oriented hydrotalcite film in nano and micron composite structure of claim 3, it is characterized in that: the reaction conditions of step C is to react 5～20 hours down at 50～130 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101347208A CN100406388C (en) | 2005-12-19 | 2005-12-19 | Vertically oriented hydrotalcite film in nano and micron composite structure and its preparing process |
| PCT/CN2006/001002 WO2007071130A1 (en) | 2005-12-19 | 2006-05-17 | Vertically-orientated hydrotalcite-like film having composite micro-structure and its preparation method |
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|---|---|---|---|
| CNB2005101347208A CN100406388C (en) | 2005-12-19 | 2005-12-19 | Vertically oriented hydrotalcite film in nano and micron composite structure and its preparing process |
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| CN101816950B (en) * | 2010-04-30 | 2012-05-30 | 北京化工大学 | Hydrotalcite-like structuring catalyst and method for catalytic synthesis of pseudo-ionone |
| CN102650065B (en) * | 2012-05-08 | 2014-09-10 | 淄博职业学院 | Calixarene intercalated hydrotalcite film for in-situ growth on aluminum substrate and preparation method for film |
| CN103240125B (en) * | 2013-05-21 | 2014-08-20 | 北京化工大学 | Preparation method of dye-sensitized metal sulfide semiconductor nanomaterial |
| JP5866071B2 (en) * | 2013-12-27 | 2016-02-17 | 日本碍子株式会社 | Layered double hydroxide alignment film and method for producing the same |
| CN103952720B (en) * | 2014-04-29 | 2016-03-30 | 北京化工大学 | Metal base/containing cobalt acrylic/hydrotalcite-like nano membrane electrode and preparation method thereof |
| WO2016098513A1 (en) * | 2014-12-17 | 2016-06-23 | 日本碍子株式会社 | Layered double hydroxide film and composite material containing layered double hydroxide |
| CN105018999B (en) * | 2015-07-09 | 2017-07-28 | 哈尔滨工程大学 | The method of aluminum alloy differential arc oxidation film growth in situ layered double hydroxide |
| CN105502477B (en) * | 2016-01-08 | 2017-03-22 | 西北大学 | Preparation method of morphology-controllable large-area nanometer platy zinc-aluminum type hydrotalcite |
| CN106086992B (en) * | 2016-06-07 | 2018-06-29 | 重庆大学 | A kind of preparation method of the double hydroxy metal oxide closing film layers of Mg alloy surface |
| CN107913723B (en) * | 2017-12-08 | 2020-06-23 | 山东理工大学 | Chromium-containing three-dimensional nickel-aluminum hydrotalcite-like film and preparation method and application thereof |
| CN108097058B (en) * | 2017-12-29 | 2019-11-22 | 北京化工大学 | A kind of carbon dioxide selectivity osmotic membrane and its preparation method and application |
| CN109735887B (en) * | 2019-03-21 | 2021-03-30 | 福州大学 | Preparation method of magnesium alloy magnesium-manganese hydrotalcite/micro-arc oxidation corrosion-resistant coating |
| CN112354513A (en) * | 2020-11-09 | 2021-02-12 | 榆林学院 | Zn2+-Al3+-CO32-LDHs @ Al adsorbing material and application thereof in adsorbing fluorine ions by recycling |
| CN113663743B (en) * | 2021-08-20 | 2022-10-18 | 浙江大学 | Preparation and application of LDHs-based anion selective membrane |
| CN116042293A (en) * | 2023-02-11 | 2023-05-02 | 道骐科技有限公司 | Multifunctional lubricating grease and preparation method thereof |
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| JP2001002408A (en) * | 1998-12-01 | 2001-01-09 | Kyowa Chem Ind Co Ltd | Hydrotalcite-based compound having at least one of silicon-, phosphorus- and boron-based poly-oxoacid anions and at least one other anion as part and/or all of intercalated anions, its production, ir absorber for agricultural film and agricultural film containing the absorber |
| CN1507944A (en) * | 2002-12-18 | 2004-06-30 | 北京化工大学 | Method for clean synthesizing magnesite-alumina hydrotalcite |
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| US5399329A (en) * | 1993-07-06 | 1995-03-21 | Aristech Chemical Corporation | Hydrotalcite-like materials having a sheet-like morphology and process for production thereof |
| US6846870B2 (en) * | 2001-08-23 | 2005-01-25 | Sunoco, Inc. (R&M) | Hydrotalcites, syntheses, and uses |
| CN100382890C (en) * | 2005-12-06 | 2008-04-23 | 北京化工大学 | Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001002408A (en) * | 1998-12-01 | 2001-01-09 | Kyowa Chem Ind Co Ltd | Hydrotalcite-based compound having at least one of silicon-, phosphorus- and boron-based poly-oxoacid anions and at least one other anion as part and/or all of intercalated anions, its production, ir absorber for agricultural film and agricultural film containing the absorber |
| CN1507944A (en) * | 2002-12-18 | 2004-06-30 | 北京化工大学 | Method for clean synthesizing magnesite-alumina hydrotalcite |
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| WO2007071130A1 (en) | 2007-06-28 |
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