CN102817040A - A kind of electrochemical synthesis method of aluminum phosphorus molecular sieve membrane - Google Patents
A kind of electrochemical synthesis method of aluminum phosphorus molecular sieve membrane Download PDFInfo
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- CN102817040A CN102817040A CN2012102531400A CN201210253140A CN102817040A CN 102817040 A CN102817040 A CN 102817040A CN 2012102531400 A CN2012102531400 A CN 2012102531400A CN 201210253140 A CN201210253140 A CN 201210253140A CN 102817040 A CN102817040 A CN 102817040A
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Abstract
一种磷铝分子筛膜的电化学合成方法，采用三电极体系或二电极体系，将基底和合成液置于反应瓶中，采用恒电位法或线性扫描法或脉冲电流法或恒电流法进行电化学合成反应，反应后取出基底，吹干，烘干。本发明合成方法简单、快速。采用本发明方法合成的分子筛膜致密性好，通过调节合成参数，如电压、电流、温度、合成液各组分的浓度等可以对分子筛膜进行可控合成。该分子筛膜合成方法重复性高，适于工业放大。An electrochemical synthesis method of phosphorus aluminum molecular sieve membrane, using a three-electrode system or a two-electrode system, placing a substrate and a synthesis solution in a reaction bottle, and using a constant potential method or a linear scanning method or a pulse current method or a constant current method to conduct electrochemistry. Chemical synthesis reaction, take out the substrate after the reaction, blow dry, and dry. The synthetic method of the present invention is simple and rapid. The molecular sieve membrane synthesized by the method of the invention has good compactness, and the molecular sieve membrane can be controllably synthesized by adjusting synthesis parameters, such as voltage, current, temperature, concentration of each component of the synthesis liquid, and the like. The molecular sieve membrane synthesis method has high repeatability and is suitable for industrial scale-up.
Description
Technical field
The present invention relates to the synthetic and Application Areas of molecular screen membrane, a kind of electrochemical method for synthesizing of phosphate aluminium molecular sieve film is provided especially.
Background technology
Molecular sieve is one type of crystal with homogeneous duct size.And by the molecular screen membrane that molecular sieve crystal assembles, have a wide range of applications in fields such as catalysis, separation and IXs.Especially because its less energy-consumption, pollution-free, separating size is high and can separate continuously etc., and advantage makes it that extraordinary using value arranged aspect membrane sepn.For example 1999, Japan introduced the NaA molecular screen membrane to the market, is used for the dehydration of water-Virahol and water-ethanol system, has realized the industrial applications of zeolite molecular sieve film large assemblies device first.Over past ten years, molecular screen membrane is because its Adjustable structure, forms controlled, good thermostability and chemicalstability, characteristics such as nontoxic make molecular screen membrane have and do not rely on the otherwise application that it sieves character.For example scientists is applied to molecular screen membrane frontiers such as hydrophilic sterilization coating, the rotten Tu Ceng ﹑ microelectronic chip low-k coating of Fang and erosion resistant coating.But up to the present, the industrial demonstration unit of several places based on the molecular screen membrane separation performance only arranged in the world, and other types of applications still is in the laboratory study stage.
The topmost technical barrier that hinders the molecular screen membrane industrial applications at present is how to utilize simple method to synthesize does not have defective, the molecular screen membrane of high orientation.
In the synthetic field of molecular screen membrane tradition, simply the most also be that compound method is a hydrothermal synthesis method the most widely.It is after preparing the synthetic liquid of molecular screen membrane, substrate directly is dipped in the synthetic liquid, and under hydrothermal synthesizing condition, the control proper reaction conditions, like temperature, pressure and generated time etc. go out the method for molecular screen membrane in the substrate surface direct growth.This method technological process is simple, need not modify in advance carrier, and cost is low, and the shape of substrate is not limited, thereby helps the industrialized mass production molecular screen membrane.But its disadvantage is the common defectiveness of molecular screen membrane that synthesizes, and poor orientation, and this has brought very big difficulty with regard to the practical application of giving molecular screen membrane.And crystal seed method is the diauxic growth method again, and these defectives develop out in order to remedy just.These class methods are separated nucleation process and film process, and at first through dip-coating, methods such as spin coating are decorating molecule sieve crystal seed in substrate, makes crystal seed layer.The substrate that will contain crystal seed layer is then immersed in the synthetic liquid of secondary, generally makes the seeded growth film forming through hydrothermal treatment consists.This method can significantly reduce the quantity of defective in the film, and prepares the molecular screen membrane of height-oriented property through accurately controlling nucleation and film process.The crystal seed method step is more, and crystal seed is had relatively high expectations, and like the necessary big or small homogeneous of crystal seed, is evenly distributed, and between crystal seed layer and the carrier enough bonding forces etc. will be arranged.Particularly in big area or complicated shape substrate when synthetic, because the defective of crystal seed layer or come off there is defective in the molecular screen membrane that causes synthesizing, thereby be unfavorable for the large-scale commercial prodn of molecular screen membrane.
Electrophoretic deposition has been widely used in the preparation and research of industrial ceramics film, but is directed against the synthetic of molecular screen membrane, and the electrophoretic deposition of report only limits to the preparation of molecular sieve crystal seed layer at present.This method is under the driving of extra electric field (voltage is about 40V), makes the charged particle directional migration to substrate surface, prepares densification, be orientated controlled, the crystal seed layer that thickness is adjustable.But, then must under the condition of hydro-thermal, further handle film forming if will prepare the molecular screen membrane of continuous densification.Because the HTHP of hydrothermal method must carry out in encloses container, be applied in this individual system electric field arrangement relatively more difficult.The electrochemical window very narrow (being approximately 1.2V) of aqueous solvent simultaneously, and impressed voltage can not surpass 2V usually in case water by electrolysis, so this method has received great restriction in the application of molecular screen membrane aspect synthesizing.
The ion thermal synthesis that with the ionic liquid is solvent then can address the above problem well.The work of ion thermal synthesis at present mainly concentrated on synthesizing of molecular sieve crystal; Scientists also is applied to the ion thermal synthesis in the preparation of molecular screen membrane recently, and successfully synthesizes AEL type molecular screen membrane with better antiseptic property and the phosphate aluminium molecular sieve film with separation function.Because ion liquid electrochemical window is very wide, electroconductibility and chemistry and thermodynamic stability are also quite high.The at high temperature extremely low vp of ionic liquid makes the synthetic of molecular sieve (film) in open container, to carry out simultaneously.So ion liquid these characteristics help to overcome electric field is applied to insurmountable difficulty in the hydro-thermal building-up process, can expects: electrochemical method is applied in the ionic liquid synthetic system, can synthesizes the phosphate aluminium molecular sieve film at least.This compound method is different from simple ion thermal synthesis because extra electric field is arranged.Also be different from electrophoretic deposition (reaction suspension of electrophoretic deposition is to contain charged ion) or strike (process that metals ion is separated out at negative electrode).We are with this method called after electrochemical ion thermal synthesis method.
The present invention makes full use of the simple of electrochemical method; Controlled, easy characteristics of amplifying, and the chemistry of ionic liquid height; Extremely low vp and wide characteristics such as electrochemical window under thermodynamic stability, the high temperature; Not only can be used as solvent but also can be used as template and need not to introduce advantage such as additional template agent at synthetic intermediate ion liquid self, adopted the electrochemical ion thermal synthesis method, through regulating synthetic parameters; Like voltage, electric current, temperature, synthetic each component concentrations of liquid etc.; Through containing surperficial aluminium of aluminium substrate or the aluminium in the synthetic liquid as the aluminium source, can carry out controlledly synthesis to the orientation and the pattern of molecular screen membrane, carry out application simultaneously like aspects such as anticorrosion or separation.Adopt the inventive method synthetic molecular screen membrane compactness good, this molecular screen membrane compound method repeatability is high, is suitable for industry and amplifies.
Summary of the invention
The object of the present invention is to provide a kind of phosphate aluminium molecular sieve film (AlPO
4-n) electrochemical method for synthesizing, the molecular screen membrane that this method synthesizes has good compactness, and synthetic have a high duplication.
The invention provides a kind of electrochemical method for synthesizing of phosphate aluminium molecular sieve film; Adopt three-electrode system or two electrode systems; Substrate and synthetic liquid are placed reaction flask, adopt potentiostatic method or linear time base sweep method or pulse current method or galvanostatic method to carry out the electrochemical synthesis reaction, substrate is taken out in the reaction back; Dry up oven dry.
The electrochemical method for synthesizing of phosphate aluminium molecular sieve film provided by the invention, said constant potential U=-100V～+ 100V; Said continuous current I=-0.01nA～10A; Said linear time base sweep method initial voltage U=-100V～+ 100V, final voltage U=-100V～+ 100V, the scanning speed scope is 5mV/s～250mV/s; Said pulse current method can be monopulse electric current, two pulse electric current, multipulse electric current; Said monopulse electric current peak current density j=25mA/cm
2～1000A/cm
2, PW is 10min～1h, the recurrent interval is 5s～10min; Said two pulse electric current output waveform is square wave or direct current, short pulse charging current i
1=0.5A～1000A, duration of charging t
1=0.5us～1us, second pulsed current i
2=1mA～10A, duration of charging t
2=2s～9999s; Said multipulse electric current, pulse-repetition are 5～5000Hz, and pulse duty factor is 0～100%, and the forward and reverse impulse commutation time is 0～9999ms, and each organizes current duration is 1s≤t
1, t
2～t
10≤9999s, peak inrush current are 1A～1000A; Temperature of reaction T=130 ℃～290 ℃ of said electrochemical synthesis reaction, synthesising reacting time t=0.1～48 hour.
The electrochemical method for synthesizing of phosphate aluminium molecular sieve film provided by the invention, said synthetic liquid consist of a IL:b PO
4 3-: cF
-: d Al
3+, wherein IL is an ionic liquid, ion liquid negatively charged ion is Cl
-, Br
-, I
-, [BF
4]
-, [AlCl
4]
-, [Al
2Cl
7]
-, [Al
2Br
7]
-, [PF
6]
-, [NO
3]
-, [NO
2]
-, [CH
3COO]
-, [SO
4] 2
-, [CF
3SO
3]
-, [CF
3CO
2]
-, [N (SO
2CF
3)
2]
-, [N (CN)
2]
-, [CB
11H
6Cl
6]
-, [CH
3CB
11H
11]
-, [C
2H
5CB
11H
11]-in one or more; Ion liquid positively charged ion is substituted tetraalkyl amine positively charged ion or substituted pyridinium ion or substituted glyoxaline cation; Like 1-methyl-3-Methylimidazole positively charged ion, 1-ethyl-3-Methylimidazole positively charged ion, 1-propyl group-3-Methylimidazole positively charged ion, 1-sec.-propyl-3-Methylimidazole positively charged ion, 1-butyl-3-Methylimidazole positively charged ion, 1-amyl group-3-Methylimidazole positively charged ion, 1; 1 '-dimethyl--3,3 '-in the hexanaphthene diimidazole positively charged ion, 1-methoxyethyl-3-Methylimidazole positively charged ion one or more; The phosphorus source is the phosphorus containg substances of phosphoric acid or primary ammonium phosphate or Secondary ammonium phosphate or phosphagel phosphaljel; The fluorine source is hydrofluoric acid or Neutral ammonium fluoride or Sodium Fluoride or hydrogen fluoride-pyridine complex compound or the fluorine-containing material of fluoridizing triethylammonium tetrakis, the aluminium source be aluminium powder or aluminum bromide or sodium metaaluminate or sodium aluminate or or the aluminium-containing substance of pseudo-boehmite or white lake or aluminum isopropylate; A=0.01～1000, b=0.01～1000, c=0.01～1000, d=0～1000.
Each composition that the electrochemical method for synthesizing of phosphate aluminium molecular sieve film provided by the invention, being formulated as of said synthetic liquid will synthesize liquid mixes and is incorporated in 20～130 ℃ and stirred 0～10 hour.
The electrochemical method for synthesizing of phosphate aluminium molecular sieve film provided by the invention, said three-electrode system comprises working electrode, counter electrode, reference electrode; Working electrode and counter electrode are made up of substrate; Reference electrode is Ag/AgBr or Pt or SCE SCE; Synthetic liquid provides the aluminium source.In the three-electrode system, when working electrode or counter electrode when containing the Al substrate, containing the Al substrate is that pure Al sheet, surface contain Al
2O
3Electro-conductive material, the ceramic monolith of surface sputtering metal Al layer, duraluminum, surface be coated with in the electro-conductive materials such as metal or alloy of aluminium lamination one or more.
The electrochemical method for synthesizing of phosphate aluminium molecular sieve film provided by the invention, said two electrode systems comprise working electrode, counter electrode; Working electrode and counter electrode are made up of substrate; Synthetic liquid provides the aluminium source.In two electrode systems, when working electrode or counter electrode when containing the Al substrate, containing the Al substrate is that pure Al sheet, surface contain Al
2O
3Electro-conductive material, the ceramic monolith of surface sputtering metal Al layer, duraluminum, surface be coated with in the electro-conductive materials such as metal or alloy of aluminium lamination one or more.
Electrochemical method among the present invention comprises the constant potential method, the continuous current method, and the linear time base sweep method, pulse current method, the substrate of the synthesizing molecular sieve film that provides is that metal or alloy, the surface that pure Al, duraluminum, surface are coated with aluminium contains aluminium element such as Al
2O
3Electro-conductive material, the electro-conductive materials such as ceramic monolith of surface sputtering metal Al layer.This compound method is simple, and fast, repeatability is high, and can carry out controlled modulation to the pattern of molecular screen membrane, is easy to industriallization and amplifies.
Description of drawings
Fig. 1 is AlPO
4The preparation flow synoptic diagram of-n type molecular screen membrane;
Fig. 2 is the device synoptic diagram of embodiment 1 three-electrode system synthesizing molecular sieve film;
Fig. 3 is the x-ray diffraction pattern of embodiment 1 synthesizing molecular sieve film;
Fig. 4 is the scanning electron microscope diagram on embodiment 1 synthesizing molecular sieve film surface;
Fig. 5 is the scanning electron microscope diagram on embodiment 3 synthesizing molecular sieve films surface;
Fig. 6 is the scanning electron microscope diagram on embodiment 5 synthesizing molecular sieve films surface;
Fig. 7 is the scanning electron microscope diagram on embodiment 6 synthesizing molecular sieve films surface;
Fig. 8 is the X-ray diffractogram of embodiment 7 synthesizing molecular sieve films;
Fig. 9 is the scanning electron microscope diagram of embodiment 8 synthesizing molecular sieve films;
Figure 10 is the scanning electron microscope diagram of embodiment 8 synthesizing molecular sieve films;
Figure 11 is the scanning electron microscope diagram of embodiment 9 synthesizing molecular sieve films;
Figure 12 is the scanning electron microscope diagram of embodiment 10 synthesizing molecular sieve films;
Figure 13 is the scanning electron microscope diagram of embodiment 11 synthesizing molecular sieve films;
Figure 14 is the scanning electron microscope diagram of embodiment 12 synthesizing molecular sieve films;
Figure 15 is the DC polarization curve of embodiment 1 synthetic molecular screen membrane in 0.1M NaCl solution.
Embodiment
Following embodiment will further explain the present invention, but therefore not limit the present invention.
The used substrate of synthesizing molecular sieve film is the fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Before substrate is used in acetone ultrasonic washing, dry up subsequent use then with high-pressure air.
The synthetic liquid of synthesizing molecular sieve film disposes as follows:
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ° of C heated and stirred 1 hour.
2 fine aluminium sheets vertically are positioned in the uncovered reaction flask respectively as working electrode and counter electrode; Reference electrode is Pt, will synthesize liquid and pour in the reaction flask, and system is heated to 190 ° of C; Adopt potentiostatic method; Voltage is set is-0.2V (vs. reference electrode), and generated time is 4h, and experimental installation is as shown in Figure 2; Aluminium flake after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.The molecular screen membrane that obtains on the working electrode is an AEL type molecular screen membrane (shown in Figure 3) through the X-ray diffraction levies in kind.Can find out the AlPO of preparation from the electron scanning micrograph
4It is tightly packed that-11 molecular screen membranes present petal-shaped, has very high compactness, and film itself and molecular sieve crystal duct orientation all is tiled in substrate surface, demonstrates completely orientation (shown in Figure 4) in the face.
Embodiment 2 AlPO
4The preparation of-11 molecular screen membranes
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ℃ of heated and stirred 1 hour.
2 fine aluminium sheets vertically are positioned in the uncovered reaction flask respectively as working electrode and counter electrode, and reference electrode is Pt, will synthesize liquid and pour in the reaction flask, and system is heated to 190 ° of C, adopts galvanostatic method, and it is 10nA that electric current is set, and generated time is 4h.Aluminium flake after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.It is the AEL structure that the molecular sieve XRD that on working electrode Al sheet, grows confirms, electron scanning micrograph finds that film is continuously fine and close, and presents orientation in the very high face, but the crystal grain size is less.(shown in Figure 6).
Press embodiment 2 identical operations, just change the test value of continuous current: the used substrate of synthesizing molecular sieve film is the fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Before substrate is used in acetone ultrasonic washing, dry up subsequent use then with high-pressure air.
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ℃ of heated and stirred 1 hour.
2 fine aluminium sheets vertically are positioned in the uncovered reaction flask respectively as working electrode and counter electrode, and reference electrode is Pt, will synthesize liquid and pour in the reaction flask, and system is heated to 190 ° of C, adopts galvanostatic method, and it is 100nA that electric current is set, and generated time is 4h.It is the AEL structure that the molecular sieve XRD that on working electrode Al sheet, grows confirms, electron scanning micrograph finds, is the petal-shaped of semi-closure and bar-shaped, and film is continuously fine and close, but demonstrates completely orientation in the face.
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ° of C heated and stirred 1 hour.
2 fine aluminium sheets vertically are positioned in the uncovered reaction flask respectively as working electrode and counter electrode, and reference electrode is Pt, will synthesize liquid and pour in the reaction flask; System is heated to 190 ° of C; Adopt potentiostatic method, it is-0.2V (vs. reference electrode) that generated time is 6h that voltage is set.Aluminium flake after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.The molecular screen membrane of synthetic gained is continuously fine and close, is petal-shaped, be orientated outward with face with orientation in the face simultaneously, but being oriented to the master in the face, and the dephasign generation is arranged.(shown in Figure 7).
0.51g is restrained phosphoric acid and 0.06g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ° of C heated and stirred 1 hour.
2 fine aluminium sheets vertically are positioned in the uncovered reaction flask respectively as working electrode and counter electrode, and reference electrode is Pt, will synthesize liquid and pour in the reaction flask; System is heated to 190 ° of C; Adopt potentiostatic method, it is-0.2V (vs. reference electrode) that generated time is 4h that voltage is set.Aluminium flake after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.The molecular screen membrane of synthetic gained is continuously fine and close, sea cucumber shape and coccoid crystal is arranged, but be oriented to the master outward with face.(shown in Figure 8).
Press embodiment 1 identical operations, just the substrate that synthesizing molecular sieve film is used changes flaky aluminum alloy A A2204-T3 into, and potentiostatic method is changed into galvanostatic method: duraluminum is long to be 37mm, and wide is 18mm.Basement membrane polishes flat with spun yarn paper before using, ultrasonic washing in the acetone, and high-pressure air dries up subsequent use then.
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ° of C heated and stirred 1 hour.
2 aluminum alloy sheets vertically are positioned in the uncovered reaction flask respectively as working electrode and counter electrode, and reference electrode is Pt, will synthesize liquid and pour in the reaction flask; System is heated to 190 ° of C; Adopt potentiostatic method, it is-0.2V (vs. reference electrode) that generated time is 4h that voltage is set.Aluminum alloy sheet after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.Fig. 9 is an electron scanning micrograph, can see that membrane is continuously fine and close, is bar-shaped and petal-shaped, but does not have orientation in the complete face.
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ° of C heated and stirred 1 hour.
2 fine aluminium sheets vertically are positioned in the uncovered reaction flask respectively as working electrode and counter electrode, and reference electrode is Pt, will synthesize liquid and pour in the reaction flask; System is heated to 190 ° of C; Adopt potentiostatic method, voltage is set is-0.2V (vs. reference electrode) generated time 4h.Aluminium flake after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.The molecular screen membrane that obtains is an AFI type molecular screen membrane (shown in figure 10) through the X-ray diffraction levies in kind.Can see that membrane is continuously fine and close from the electron scanning micrograph, present thin petal-shaped (shown in Figure 11), and film itself and crystal duct orientation thereof all be tiled in substrate surface, present the interior growth orientation property of higher face.
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ° of C heated and stirred 1 hour.
2 fine aluminium sheets vertically are positioned in the uncovered reaction flask respectively as working electrode and counter electrode, and reference electrode is Pt, will synthesize liquid and pour in the reaction flask; System is heated to 175 ° of C; Adopt potentiostatic method, voltage is set is-0.2V (vs. reference electrode) generated time 4h.Aluminium flake after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.The molecular screen membrane of synthetic gained is continuously fine and close, presents bar-shaped and thin petal-shaped, is mixed and disorderly orientation.(shown in Figure 12).
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ° of C heated and stirred 1 hour.
Be positioned in the uncovered reaction flask respectively as working electrode and counter electrode 1 fine aluminium sheet is vertical with the Pt silk, reference electrode is Pt, will synthesize liquid and pour in the reaction flask; System is heated to 190 ° of C; Adopt potentiostatic method, voltage is set is-0.2V (vs. reference electrode) generated time 4h.Aluminium flake after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.From electron scanning micrograph, can see that membrane presents thin petal-shaped, but also discontinuous densification neither be orientated (shown in Figure 13) in the complete face.
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ° of C heated and stirred 1 hour.
2 fine aluminium sheets are positioned in the uncovered reaction flask respectively as working electrode and counter electrode, and reference electrode is Pt, will synthesize liquid and pour in the reaction flask; System is heated to 190 ° of C; Adopt potentiostatic method, voltage is set is-0.2V (vs. reference electrode) generated time 4h.Aluminium flake after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.The molecular screen membrane that obtains is shown in figure 14.From electron scanning micrograph, can see the continuously fine and close of membrane, but have a small amount of outgrowth oriented crystal to exist.
Embodiment 11 AlPO
4The preparation of-11 molecular screen membranes
1.7g is restrained phosphoric acid and 0.2g gram HF join in 32g gram 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 ° of C heated and stirred 1 hour.
2 fine aluminium sheets vertically are positioned in the uncovered reaction flask respectively as working electrode and counter electrode.To synthesize liquid and pour in the reaction flask, system is heated to 190 ° of C, adopts two electrode systems, and potentiostatic method is provided with voltage and is-9V generated time 8h; Aluminium flake after synthetic is through deionized water wash, and high-pressure air dries up, and 60 ° of C oven for drying are spent the night then.From electron scanning micrograph, can see that membrane is fine and close, but not demonstrate the outer orientation of height face, but interior orientation of face and the outer orientation of face all exist.(shown in Figure 15).
The test of embodiment 12 antiseptic properties
Corrosive fluid is the 0.1M NaCl aqueous solution.Corrosive fluid is poured in the corrosion pond, and working electrode is the molecular sieve diaphragm of exposed aluminium flake or embodiment 2 preparations, and counter electrode is the Pt sheet, and reference electrode is (Ag.AgCl)/KCl (3.5M).Before the test corrosion, molecular sieve is stablized 30min in corrosive fluid, carries out the scanning of DC polarization curve then, sweep limit-0.5V～0.5V, sweep velocity 10mV/min.The result is shown in figure 15.Demonstration is fine and close by the electrochemical method synthetic, and in the height inner face molecular screen membrane of orientation has excellent antiseptic property.
Comparative example 1
Document (R.Cai, M.W.Sun, Z.W.Chen, R.Munoz, C.O ' neill, D.E.Beving, Y.S.Yan, Angew.Chem.Int.Ed.2008,47,525) has been reported the SAPO-11 molecular screen membrane of ion thermal synthesis method preparation.Interpolation through Si reduces the crystalline speed of growth, makes the final SAPO-11 that obtains have the c-axle orientation of height, promptly in the film crystal duct perpendicular to substrate surface.DC polarization curve in 0.1M NaCl corrosive fluid demonstrates, and antiseptic property is parallel to the AlPO of substrate surface not as prepared crystal duct among the present invention
4-n molecular screen membrane.
Claims (15)
1. the electrochemical method for synthesizing of a phosphate aluminium molecular sieve film; It is characterized in that: adopt three-electrode system or two electrode systems; Substrate and synthetic liquid are placed reaction flask, adopt potentiostatic method or linear time base sweep method or pulse current method or galvanostatic method to carry out the electrochemical synthesis reaction, substrate is taken out in the reaction back; Dry up oven dry.
2. according to the electrochemical method for synthesizing of the said phosphate aluminium molecular sieve film of claim 1, it is characterized in that: said constant potential U=-100V～+ 100V.
3. according to the electrochemical method for synthesizing of the said phosphate aluminium molecular sieve film of claim 1, it is characterized in that: said continuous current I=-0.01nA～10A.
4. according to the electrochemical method for synthesizing of the said phosphate aluminium molecular sieve film of claim 1, it is characterized in that: said linear time base sweep method initial voltage U=-100V～+ 100V, final voltage U=-100V～+ 100V, the scanning speed scope is 5mV/s～250mV/s.
5. according to the electrochemical method for synthesizing of the said phosphate aluminium molecular sieve film of claim 1, it is characterized in that: said pulse current method is the monopulse electric current, peak current density j=25mA/cm
2～1000A/cm
2, PW is 10min～1h, the recurrent interval is 5s～10min.
6. according to the electrochemical method for synthesizing of the said phosphate aluminium molecular sieve film of claim 1, it is characterized in that: said pulse current method is the two pulse electric current, short pulse charging current i
1=0.5A～1000A, duration of charging t
1=0.5us～1us, second pulsed current i
2=1mA～10A, duration of charging t
2=2s～9999s.
7. according to the electrochemical method for synthesizing of the said phosphate aluminium molecular sieve film of claim 1; It is characterized in that: said pulse current method is the multipulse electric current; Pulse-repetition is 5～5000Hz; Pulse duty factor is 0～100%, and the forward and reverse impulse commutation time is 0～9999ms, and each organizes current duration is 1s≤t
1, t
2～t
10≤9999s, peak inrush current are 1A～1000A.
8. according to the electrochemical method for synthesizing of the said phosphate aluminium molecular sieve film of claim 1, it is characterized in that: the temperature of reaction T=130oC～290oC of said electrochemical synthesis reaction, synthesising reacting time t=0.1～48 hour.
9. according to the electrochemical method for synthesizing of the said phosphate aluminium molecular sieve film of claim 1, it is characterized in that: said synthetic liquid consist of a IL:b PO
4 3-: cF
-: d Al
3+, wherein IL is an ionic liquid, ion liquid negatively charged ion is Cl
-, Br
-, I
-, [BF
4]
-, [AlCl
4]
-, [Al
2Cl
7]
-, [Al
2Br
7]
-, [PF
6]
-, [NO
3]
-, [NO
2]
-, [CH
3COO]
-, [SO
4] 2
-, [CF
3SO
3]
-, [CF
3CO
2]
-, [N (SO
2CF
3)
2]
-, [N (CN)
2]
-, [CB
11H
6Cl
6]
-, [CH
3CB
11H
11]
-, [C
2H
5CB
11H
11]
-In one or more; Ion liquid positively charged ion is substituted tetraalkyl amine positively charged ion or substituted pyridinium ion or substituted glyoxaline cation; The phosphorus source is the phosphorus containg substances of phosphoric acid or primary ammonium phosphate or Secondary ammonium phosphate or phosphagel phosphaljel; The fluorine source is hydrofluoric acid or Neutral ammonium fluoride or Sodium Fluoride or hydrogen fluoride-pyridine complex compound or the fluorine-containing material of fluoridizing triethylammonium tetrakis, and the aluminium source is the aluminium-containing substance of aluminium powder or aluminum bromide or sodium metaaluminate or sodium aluminate or pseudo-boehmite or white lake or aluminum isopropylate; A=0.01 ~ 1000, b=0.01 ~ 1000, c=0.01 ~ 1000, d=0 ~ 1000.
10. according to the electrochemical method for synthesizing of the said phosphate aluminium molecular sieve film of claim 1; It is characterized in that: said substituted glyoxaline cation is 1-methyl-3-Methylimidazole positively charged ion, 1-ethyl-3-Methylimidazole positively charged ion, 1-propyl group-3-Methylimidazole positively charged ion, 1-sec.-propyl-3-Methylimidazole positively charged ion, 1-butyl-3-Methylimidazole positively charged ion, 1-amyl group-3-Methylimidazole positively charged ion, 1; In 1 ＇-dimethyl--3,3 ＇-hexanaphthene diimidazole positively charged ion, the 1-methoxyethyl-3-Methylimidazole positively charged ion one or more.
11. the electrochemical method for synthesizing according to claim 1 or 9 said phosphate aluminium molecular sieve films is characterized in that: the mixed 20 ~ 130oC that is incorporated in of each composition that will synthesize liquid that is formulated as of said synthetic liquid stirred 0 ~ 10 hour.
12. the electrochemical method for synthesizing according to the said phosphate aluminium molecular sieve film of claim 1 is characterized in that: said three-electrode system comprises working electrode, counter electrode, reference electrode; Working electrode and counter electrode are made up of substrate; Reference electrode is Ag/AgBr or Pt or SCE SCE; Synthetic liquid provides the aluminium source.
13. the electrochemical method for synthesizing according to claim 1 or 12 said phosphate aluminium molecular sieve films is characterized in that: in the three-electrode system, working electrode or counter electrode are for containing the Al substrate; Containing the Al substrate is that pure Al sheet, surface contain Al
2O
3Electro-conductive material, the ceramic monolith of surface sputtering metal Al layer, duraluminum, surface be coated with in the metal or alloy electro-conductive material of aluminium lamination one or more.
14. the electrochemical method for synthesizing according to the said phosphate aluminium molecular sieve film of claim 1 is characterized in that: said two electrode systems comprise working electrode, counter electrode; Working electrode and counter electrode are made up of substrate; Synthetic liquid provides the aluminium source.
15. the electrochemical method for synthesizing according to claim 1 or 14 said phosphate aluminium molecular sieve films is characterized in that: in two electrode systems, working electrode or counter electrode are for containing the Al substrate; Containing the Al substrate is that pure Al sheet, surface contain Al
2O
3Electro-conductive material, the ceramic monolith of surface sputtering metal Al layer, duraluminum, surface be coated with in the metal or alloy electro-conductive material of aluminium lamination one or more.
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