CN102817040B - Electrochemical synthetic method for phosphorus aluminum molecular sieve membrane - Google Patents
Electrochemical synthetic method for phosphorus aluminum molecular sieve membrane Download PDFInfo
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Abstract
The invention provides an electrochemical synthetic method for a phosphorus aluminum molecular sieve membrane. According to the invention, a three-electrode system or a two-electrode system is employed, a substrate and synthesis fluid are placed in a reaction bottle, an electrochemical synthetic reaction is carried out by using a constant potential method, a linear scanning method, a pulse current method or a constant current method, and the substrate is taken out after the reaction and undergoes blow-drying and stoving. The synthetic method provided by the invention is simple and fast. The molecular sieve membrane synthesized by using the method provided by the invention has good compactness; controllable synthesis of the molecular sieve membrane can be realized by adjusting synthesis parameters, e.g., voltage, current, temperature, concentration of each component in the synthesis fluid, etc. The synthetic method for the molecular sieve membrane has high repeatability and is suitable for industrial scale-up.
Description
Technical field
The present invention relates to synthesis and the Application Areas of molecular screen membrane, specifically provide a kind of electrochemical method for synthesizing of phosphate aluminium molecular sieve film.
Background technology
Molecular sieve is the crystal that a class has homogeneous pore size.And the molecular screen membrane assembled by molecular sieve crystal, have a wide range of applications in fields such as catalysis, separation and ion-exchanges.Especially due to its less energy-consumption, pollution-free, resolution is high and can carry out the advantage such as being continuously separated and make it in membrane sepn, have extraordinary using value.Such as 1999, Japan introduced NaA molecular sieve membrane to the market, for the dehydration of water-Virahol and water-ethanol system, achieved the industrial applications of zeolite molecular sieve film large assemblies device first.Nearly ten years, molecular screen membrane due to its structure adjustable, form controlled, good thermostability and chemical stability, the feature such as nontoxic, molecular screen membrane had do not rely on the otherwise application of its screening character.Molecular screen membrane is applied to the frontiers such as hydrophilic sterilization coating, corrosion protection coating, microelectronic chip low-k coating and erosion resistant coating by such as scientists.But up to the present, only there is a few place in the world based on the industrial demonstration unit of molecular screen membrane separation performance, and other types of applications, be still in the laboratory study stage.
The topmost technical barrier of current obstruction molecular screen membrane industrial applications is that how utilizing simple method to synthesize does not have defect, the molecular screen membrane of high orientation.
The most traditional in molecular screen membrane synthesis field, the simplest is also that synthetic method is hydrothermal synthesis method the most widely.It is that substrate be directly dipped in synthesis liquid, under hydrothermal synthesizing condition, control suitable reaction conditions, as temperature, pressure and generated time etc., go out the method for molecular screen membrane in substrate surface direct growth after preparing molecular screen membrane synthesis liquid.This method technological process is simple, and do not need to modify in advance carrier, cost is low, and does not limit the shape of substrate, thus is conducive to industrialized mass production molecular screen membrane.But its disadvantage is the usual defectiveness of molecular screen membrane synthesized, and poor orientation, this brings very large difficulty with regard to giving the practical application of molecular screen membrane.And crystal seed method, be again secondary growth method, in order to make up, these defects develop out just.Nucleation process and film process are separated by these class methods, and first by dip-coating, the methods such as spin coating are decorating molecule sieve crystal seed in substrate, makes crystal seed layer.Then the substrate containing crystal seed layer is immersed in secondary synthesis liquid, generally make seeded growth film forming by hydrothermal treatment consists.The method can greatly reduce the quantity of defect in film, and by accurately control nucleation and film process prepare the molecular screen membrane of height-oriented property.Crystal seed method step is more, and requires higher to crystal seed, and size as necessary in crystal seed is homogeneous, is evenly distributed, will has enough bonding forces etc. between crystal seed layer and carrier.When particularly synthesizing in big area or complicated shape substrate, due to defect or the molecular screen membrane existing defects that will cause synthesizing that comes off of crystal seed layer, be thus unfavorable for the large-scale commercial production of molecular screen membrane.
In the preparation that electrophoretic deposition has been widely used in industrial ceramics film and research, but for the synthesis of molecular screen membrane, the electrophoretic deposition of report is only limitted to the preparation of molecular sieve crystal seed layer at present.The method is under the driving of extra electric field (voltage is at about 40V), and make charged particle directional migration to substrate surface, prepare densification, orientation is controlled, the crystal seed layer that thickness is adjustable.But to prepare molecular screen membrane fine and close continuously, then under the condition of hydro-thermal, film forming must be processed further.Because the High Temperature High Pressure of hydrothermal method must be carried out in encloses container, electric field arrangement is applied in this individual system more difficult.The simultaneously electrochemical window very narrow (being approximately 1.2V) of aqueous solvent, and impressed voltage usually can not more than 2V in order to avoid water be by electrolysis, therefore the application of the method in molecular screen membrane synthesis is greatly limited.
Be that the ion thermal synthesis of solvent then can solve the problem well with ionic liquid.The work of current ion thermal synthesis mainly concentrates in the synthesis of molecular sieve crystal, ion thermal synthesis is also applied in the preparation of molecular screen membrane by nearest scientists, and successfully synthesizes the AEL type molecular screen membrane with better antiseptic property and the phosphate aluminium molecular sieve film with separation function.Because the electrochemical window of ionic liquid is very wide, electroconductibility and chemistry and thermodynamic stability also quite high.The vapour pressure that ionic liquid is at high temperature extremely low simultaneously makes the synthesis of molecular sieve (film) can carry out in open container.So these features of ionic liquid contribute to overcoming, and electric field is applied to insurmountable difficulty in Hydrothermal Synthesis process, it is expected to: electrochemical method is applied in ionic liquid synthetic system, at least can synthesizes phosphate aluminium molecular sieve film.This synthetic method is different from simple ion thermal synthesis because there being extra electric field.Also electrophoretic deposition (reaction suspension of electrophoretic deposition to contain charged ion) or strike (process that metal ion is separated out at negative electrode) is different from.We are by this method called after electrochemical ion thermal synthesis method.
The present invention makes full use of the simple of electrochemical method, controlled, the feature of easy amplification, and the chemistry of ionic liquid height, thermodynamic stability, the features such as vapour pressure extremely low under high temperature and wide electrochemical window, not only template as solvent but also can have been can be used as and without the need to introducing the advantages such as additional template agent at synthesis intermediate ion liquid self, adopt electrochemical ion thermal synthesis method, by regulating synthetic parameters, as voltage, electric current, temperature, the concentration etc. of each component of synthesis liquid, by containing aluminium substrate surface aluminium or synthesis liquid in aluminium as aluminium source, controlledly synthesis can be carried out to the orientation of molecular screen membrane and pattern, carry out the application as aspects such as anticorrosion or separation simultaneously.Adopt the molecular screen membrane compactness of the inventive method synthesis good, this molecular screen membrane synthetic 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 the method synthesizes has good compactness, synthesis there is 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 synthesis liquid are placed in reaction flask, potentiostatic method or linear scanning method or pulse current method or galvanostatic method is adopted to carry out electrochemical synthesis reaction, substrate is taken out after reaction, dry up, dry.
The electrochemical method for synthesizing of phosphate aluminium molecular sieve film provided by the invention, described constant potential U=-100V ~+100V; Described continuous current I=-0.01nA ~ 10A; Described linear scanning method initial voltage U=-100V ~+100V, final voltage U=-100V ~+100V, scanning speed scope is 5mV/s ~ 250mV/s; Described pulse current method can be single-pulse current method, two pulse electric current, multipulse electric current; Described single-pulse current method peak current density j=25mA/cm
2~ 1000A/cm
2, pulse width is 10min ~ 1h, and the recurrent interval is 5s ~ 10min; Described 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; Described multipulse electric current, pulse-repetition is 5 ~ 5000Hz, and pulse duty factor is 0 ~ 100%, and the forward and reverse impulse commutation time is 0 ~ 9999ms, and each group current duration is 1s≤t
1, t
2~ t
10≤ 9999s, peak inrush current is 1A ~ 1000A; Temperature of reaction T=130 DEG C ~ 290 DEG C of described 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, described synthesis liquid consist of a IL:b PO
4 3-: cF
-: d Al
3+, wherein IL is ionic liquid, and the negatively charged ion of ionic liquid 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; The positively charged ion of ionic liquid is the pyridinium ion of tetraalkyl amine positively charged ion or the replacement replaced or the glyoxaline cation of replacement, as 1-methyl-3-methyl imidazolium cation, 1-ethyl-3-methylimidazole positively charged ion, 1-propyl group-3-methyl imidazolium cation, 1-sec.-propyl-3-methyl imidazolium cation, 1-butyl-3-methyl imidazolium cation, 1-amyl group-3-methyl imidazolium cation, 1, one or more in 1 '-dimethyl-3,3 '-hexanaphthene diimidazole positively charged ion, 1-methoxyethyl-3-methyl imidazolium cation; Phosphorus source is the phosphorus containg substances of phosphoric acid or primary ammonium phosphate or Secondary ammonium phosphate or aluminum phosphate, fluorine source is hydrofluoric acid or Neutral ammonium fluoride or Sodium Fluoride or hydrogen fluoride-pyridine complex compound or the fluorine-containing material fluoridizing triethylammonium tetrakis, aluminium source be aluminium powder or aluminum bromide or sodium metaaluminate or sodium aluminate or or the aluminium-containing substance of pseudo-boehmite or aluminium hydroxide or aluminum isopropylate; A=0.01 ~ 1000, b=0.01 ~ 1000, c=0.01 ~ 1000, d=0 ~ 1000.
The electrochemical method for synthesizing of phosphate aluminium molecular sieve film provided by the invention, being formulated as of described synthesis liquid is incorporated in 20 ~ 130 DEG C of stirrings 0 ~ 10 hour by mixed for each composition of synthesis liquid.
The electrochemical method for synthesizing of phosphate aluminium molecular sieve film provided by the invention, described three-electrode system comprises working electrode, to electrode, reference electrode; Working electrode and electrode is made up of substrate; Reference electrode is Ag/AgBr or Pt or saturated calomel electrode SCE; Synthesis liquid provides aluminium source.In three-electrode system, being when containing Al substrate when working electrode or to electrode, is that pure Al sheet, surface are containing Al containing Al substrate
2o
3electro-conductive material, the ceramic monolith of surface sputtering metal Al layer, aluminium alloy, surface be coated with in the electro-conductive materials such as the metal or alloy of aluminium lamination one or more.
The electrochemical method for synthesizing of phosphate aluminium molecular sieve film provided by the invention, described two electrode systems comprise working electrode, to electrode; Working electrode and electrode is made up of substrate; Synthesis liquid provides aluminium source.In two electrode systems, being when containing Al substrate when working electrode or to electrode, is that pure Al sheet, surface are containing Al containing Al substrate
2o
3electro-conductive material, the ceramic monolith of surface sputtering metal Al layer, aluminium alloy, surface be coated with in the electro-conductive materials such as the metal or alloy of aluminium lamination one or more.
Electrochemical method in the present invention comprises constant potential method, constant current process, linear scanning method, pulse current method, the metal or alloy that the substrate of the synthesizing molecular sieve film provided is pure Al, aluminium alloy, surface are coated with aluminium, surface containing aluminium element as Al
2o
3electro-conductive material, surface sputtering metal Al layer the electro-conductive material such as ceramic monolith.This synthetic method is simple, and fast, repeatability is high, and can carry out controlled modulation to the pattern of molecular screen membrane, is easy to industrialization and amplifies.
Accompanying drawing explanation
Fig. 1 is AlPO
4the preparation flow schematic diagram of-N-shaped molecular screen membrane;
Fig. 2 is the device schematic 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 2-in-1 one-tenth molecular screen membrane surface;
Fig. 6 is the scanning electron microscope diagram on embodiment 4 synthesizing molecular sieve film surface;
Fig. 7 is the scanning electron microscope diagram on embodiment 5 synthesizing molecular sieve film surface;
Fig. 8 is the scanning electron microscope diagram of embodiment 6 synthesizing molecular sieve film;
Fig. 9 is the X-ray diffractogram of embodiment 7 synthesizing molecular sieve film;
Figure 10 is the scanning electron microscope diagram of embodiment 7 synthesizing molecular sieve film;
Figure 11 is the scanning electron microscope diagram of embodiment 8 synthesizing molecular sieve film;
Figure 12 is the scanning electron microscope diagram of embodiment 9 synthesizing molecular sieve film;
Figure 13 is the scanning electron microscope diagram of embodiment 10 synthesizing molecular sieve film;
Figure 14 is the scanning electron microscope diagram of embodiment 11 synthesizing molecular sieve film;
Figure 15 is the DC polarization curve of molecular screen membrane in 0.1M NaCl solution that embodiment 1 is synthesized.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1AlPO
4the preparation of-11 molecular screen membranes
Synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
The synthesis liquid of synthesizing molecular sieve film configures as follows:
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
2 fine aluminium sheets are vertically positioned in uncovered reaction flask as working electrode with to electrode, reference electrode is Pt, synthesis liquid is poured in reaction flask, system is heated to 190 DEG C, adopt potentiostatic method, arranging voltage is-0.2V(vs. reference electrode), generated time is 4h, and experimental installation is as shown in Figure 2; Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular screen membrane that working electrode obtains is AEL type molecular screen membrane (shown in Fig. 3) through X-ray diffraction levies in kind.The AlPO of preparation can be found out from 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 are all laid in substrate surface, presents orientation (shown in Fig. 4) in face completely.
Embodiment 2AlPO
4the preparation of-11 molecular screen membranes
By the operation that embodiment 1 is identical, just potentiostatic method is changed into continuous current test: synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
Vertically be positioned over as working electrode with to electrode in uncovered reaction flask using 2 fine aluminium sheets, reference electrode is Pt, pours in reaction flask by synthesis liquid, and system is heated to 190 DEG C, and adopt galvanostatic method, arranging electric current is 10nA, and generated time is 4h.Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.It is AEL structure that the molecular sieve XRD that working electrode Al sheet grows confirms, electron scanning micrograph finds, film is continuously fine and close, and presents orientation in very high face, but crystal grain size is less.(shown in Fig. 5).
Embodiment 3AlPO
4the preparation of-11 molecular screen membranes
By the operation that embodiment 2 is identical, just change the test value of continuous current: synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
Vertically be positioned over as working electrode with to electrode in uncovered reaction flask using 2 fine aluminium sheets, reference electrode is Pt, pours in reaction flask by synthesis liquid, and system is heated to 190 DEG C, and adopt galvanostatic method, arranging electric current is 100nA, and generated time is 4h.It is AEL structure that molecular sieve XRD that working electrode Al sheet grows confirms, electron scanning micrograph finds, the petal-shaped in semi-closure and bar-shaped, and film is continuously fine and close, but does not present orientation in face completely.
Embodiment 4AlPO
4the preparation of-11 molecular screen membranes
By the operation that embodiment 1 is identical, just change the electrochemical synthesis time: synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
Vertically be positioned over as working electrode with to electrode in uncovered reaction flask using 2 fine aluminium sheets, reference electrode is Pt, pours in reaction flask by synthesis liquid, system is heated to 190 DEG C, adopt potentiostatic method, arranging voltage is-0.2V(vs. reference electrode), generated time is 6h.Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular screen membrane of synthesis gained is continuously fine and close, in petal-shaped, simultaneously with orientation outside orientation in face and face, but to be oriented to master in face, and has dephasign to generate.(shown in Fig. 6).
Embodiment 5AlPO
4the preparation of-11 molecular screen membranes
By the operation that embodiment 1 is identical, just change the composition of synthesis liquid: synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
0.51g gram of phosphoric acid and 0.06g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
Vertically be positioned over as working electrode with to electrode in uncovered reaction flask using 2 fine aluminium sheets, reference electrode is Pt, pours in reaction flask by synthesis liquid, system is heated to 190 DEG C, adopt potentiostatic method, arranging voltage is-0.2V(vs. reference electrode), generated time is 4h.Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular screen membrane of synthesis gained is continuously fine and close, has sea cucumber shape and coccoid crystal, but to be oriented to master outside face.(shown in Fig. 7).
Embodiment 6AlPO
4the preparation of-11 molecular screen membranes
By the operation that embodiment 1 is identical, just change substrate used for synthesizing molecular sieve film into flaky aluminum alloy A A 2204-T3, and potentiostatic method is changed into galvanostatic method: aluminium alloy is long is 37mm, and wide is 18mm.Basement membrane polishes flat with spun yarn paper before using, and ultrasonic washing in acetone, then high-pressure air dries up for subsequent use.
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
Vertically be positioned over as working electrode with to electrode in uncovered reaction flask using 2 aluminum alloy sheets, reference electrode is Pt, pours in reaction flask by synthesis liquid, system is heated to 190 DEG C, adopt potentiostatic method, arranging voltage is-0.2V(vs. reference electrode), generated time is 4h.Aluminum alloy sheet after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.Fig. 8 is electron scanning micrograph, can see that membrane is continuously fine and close, in bar-shaped and petal-shaped, but not have orientation in complete face.
Embodiment 7AlPO
4the preparation of-5 molecular screen membranes
By the operation that embodiment 1 is identical, just ionic liquid replaces with 1-butyl-3-methyl-imidazoles bromine: synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
Vertically be positioned over as working electrode with to electrode in uncovered reaction flask using 2 fine aluminium sheets, reference electrode is Pt, pours in reaction flask by synthesis liquid, system is heated to 190 DEG C, adopt potentiostatic method, arranging voltage is-0.2V(vs. reference electrode), generated time 4h.Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular screen membrane obtained is AFI type molecular screen membrane (as shown in Figure 9) through X-ray diffraction levies in kind.Can see that from electron scanning micrograph membrane is continuously fine and close, present thin petal-shaped (shown in Figure 10), and film itself and crystal duct orientation thereof all be laid in substrate surface, present growth orientation in higher face.
Embodiment 8AlPO
4the preparation of-11 molecular screen membranes
By the operation that embodiment 1 is identical, just change the synthesis temperature of electrochemical reaction: synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
Vertically be positioned over as working electrode with to electrode in uncovered reaction flask using 2 fine aluminium sheets, reference electrode is Pt, pours in reaction flask by synthesis liquid, system is heated to 175 DEG C, adopt potentiostatic method, arranging voltage is-0.2V(vs. reference electrode), generated time 4h.Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular screen membrane of synthesis gained is continuously fine and close, presents bar-shaped and thin petal-shaped, in mixed and disorderly orientation.(shown in Figure 11).
Embodiment 9AlPO
4the preparation of-11 molecular screen membranes
By the operation that embodiment 1 is identical, just change in electrochemical reaction to electrode materials: synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
Be positioned over as working electrode with to electrode in uncovered reaction flask using vertical with Pt silk for 1 fine aluminium sheet, reference electrode is Pt, pours in reaction flask by synthesis liquid, system is heated to 190 DEG C, adopt potentiostatic method, arranging voltage is-0.2V(vs. reference electrode), generated time 4h.Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.Can see that from electron scanning micrograph membrane presents thin petal-shaped, but and discontinuous densification, neither orientation (shown in Figure 12) in complete face.
Embodiment 10AlPO
4the preparation of-11 molecular screen membranes
By the operation that embodiment 1 is identical, just add aluminium source in synthesis liquid: aluminum isopropylate: synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
Be positioned over as working electrode with to electrode in uncovered reaction flask using 2 fine aluminium sheets, reference electrode is Pt, pours in reaction flask by synthesis liquid, system is heated to 190 DEG C, adopt potentiostatic method, arranging voltage is-0.2V(vs. reference electrode), generated time 4h.Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular screen membrane obtained as shown in figure 13.Can see that from electron scanning micrograph the densification of membrane is continuous, but have a small amount of outgrowth oriented crystal to exist.
Embodiment 11AlPO
4the preparation of-11 molecular screen membranes
By the operation that embodiment 1 is identical, the three-electrode system just changing electrochemical reaction is two electrode systems, makes resultant voltage raising corresponding to the time thus: synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Ultrasonic washing in acetone before substrate uses, then dries up for subsequent use with high-pressure air.
1.7g gram of phosphoric acid and 0.2g gram of HF are joined in 32g gram of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 60 DEG C of heated and stirred 1 hour.
2 fine aluminium sheets are vertically positioned in uncovered reaction flask as working electrode with to electrode.Pour in reaction flask by synthesis liquid, system is heated to 190 DEG C, adopts two electrode systems, potentiostatic method, and arranging voltage is-9V, generated time 8h; Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.Can see that from electron scanning micrograph membrane is fine and close, but not present orientation outside height face, but in face outside orientation and face orientation all exist.(shown in Figure 14).
Embodiment 12 antiseptic property is tested
Corrosive fluid is the 0.1M NaCl aqueous solution.Poured into by corrosive fluid in corrosion pond, working electrode is molecular sieve diaphragm prepared by exposed aluminium flake or embodiment 2, and be Pt sheet to electrode, reference electrode is (Ag.AgCl)/KCl (3.5M).Before test corrosion, molecular sieve stablizes 30min in corrosive fluid, then carries out the scanning of DC polarization curve, sweep limit-0.5V ~ 0.5V, sweep velocity 10mV/min.Result as shown in figure 15.The densification that display is synthesized by electrochemical method, in height inner face, the 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) reports SAPO-11 molecular screen membrane prepared by ion thermal synthesis method.Reduced the speed of growth of crystal by the interpolation of Si, make the final SAPO-11 obtained have the c-axle orientation of height, namely in film crystal duct perpendicular to substrate surface.DC polarization curve in 0.1MNaCl corrosive fluid demonstrates, and antiseptic property is not so good as the AlPO that crystal duct prepared in the present invention is parallel to substrate surface
4-n molecular screen membrane.
Claims (8)
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 synthesis liquid are placed in reaction flask, potentiostatic method or linear scanning method or pulse current method or galvanostatic method is adopted to carry out electrochemical synthesis reaction, substrate is taken out after reaction, dry up, dry;
Described constant potential U=-100V ~+100V;
Described continuous current I=-0.01nA ~ 10A;
Described linear scanning method initial voltage U=-100V ~+100V, final voltage U=-100V ~+100V, scanning speed scope is 5mV/s ~ 250mV/s;
Described pulse current method is single-pulse current method, peak current density j=25mA/cm
2~ 1000A/cm
2, pulse width is 10min ~ 1h, and the recurrent interval is 5s ~ 10min;
Described pulse current method is two pulse electric current, short pulse charging current i
1=0.5A ~ 1000A, duration of charging t
1=0.5 μ s ~ 1 μ s, second pulsed current i
2=1mA ~ 10A, duration of charging t
2=2s ~ 9999s;
Described pulse current method is multipulse electric current, and pulse-repetition is 5 ~ 5000Hz, and pulse duty factor is 0 ~ 100%, and the forward and reverse impulse commutation time is 0 ~ 9999ms, and each group current duration is 1s≤t
1, t
2~ t
10≤ 9999s, peak inrush current is 1A ~ 1000A;
Described synthesis liquid consist of a IL:b PO
4 3-: c F
-: d Al
3+, wherein IL is ionic liquid, and the negatively charged ion of ionic liquid 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; The positively charged ion of ionic liquid is the pyridinium ion of tetraalkyl amine positively charged ion or the replacement replaced or the glyoxaline cation of replacement; Phosphorus source is the phosphorus containg substances of phosphoric acid or primary ammonium phosphate or Secondary ammonium phosphate or aluminum phosphate, fluorine source is hydrofluoric acid or Neutral ammonium fluoride or Sodium Fluoride or hydrogen fluoride-pyridine complex compound or the fluorine-containing material fluoridizing triethylammonium tetrakis, and aluminium source is the aluminium-containing substance of aluminium powder or aluminum bromide or sodium metaaluminate or sodium aluminate or pseudo-boehmite or aluminium hydroxide or aluminum isopropylate; A=0.01 ~ 1000, b=0.01 ~ 1000, c=0.01 ~ 1000, d=0 ~ 1000.
2. according to the electrochemical method for synthesizing of phosphate aluminium molecular sieve film described in claim 1, it is characterized in that: temperature of reaction T=130 DEG C ~ 290 DEG C of described electrochemical synthesis reaction, synthesising reacting time t=0.1 ~ 48 hour.
3. according to the electrochemical method for synthesizing of phosphate aluminium molecular sieve film described in claim 1, it is characterized in that: the glyoxaline cation of described replacement is 1-methyl-3-methyl imidazolium cation, 1-ethyl-3-methylimidazole positively charged ion, 1-propyl group-3-methyl imidazolium cation, 1-sec.-propyl-3-methyl imidazolium cation, 1-butyl-3-methyl imidazolium cation, 1-amyl group-3-methyl imidazolium cation, 1, one or more in 1 '-dimethyl-3,3 '-hexanaphthene diimidazole positively charged ion, 1-methoxyethyl-3-methyl imidazolium cation.
4. according to the electrochemical method for synthesizing of phosphate aluminium molecular sieve film described in claim 1, it is characterized in that: being formulated as of described synthesis liquid is incorporated in 20 ~ 130 DEG C of stirrings 0 ~ 10 hour by mixed for each composition of synthesis liquid.
5. according to the electrochemical method for synthesizing of phosphate aluminium molecular sieve film described in claim 1, it is characterized in that: described three-electrode system comprises working electrode, to electrode, reference electrode; Working electrode and electrode is made up of substrate; Reference electrode is Ag/AgBr or Pt or saturated calomel electrode SCE; Synthesis liquid provides aluminium source.
6., according to the electrochemical method for synthesizing of phosphate aluminium molecular sieve film described in claim 1 or 5, it is characterized in that: in three-electrode system, working electrode or to electrode for containing Al substrate; Be that pure Al sheet, surface are containing Al containing Al substrate
2o
3electro-conductive material, the ceramic monolith of surface sputtering metal Al layer, aluminium alloy, surface be coated with in the metal or alloy electro-conductive material of aluminium lamination one or more.
7. according to the electrochemical method for synthesizing of phosphate aluminium molecular sieve film described in claim 1, it is characterized in that: described two electrode systems comprise working electrode, to electrode; Working electrode and electrode is made up of substrate; Synthesis liquid provides aluminium source.
8. according to the electrochemical method for synthesizing of phosphate aluminium molecular sieve film described in claim 1 or 7, it is characterized in that: in two electrode systems, working electrode or to electrode for containing Al substrate; Be that pure Al sheet, surface are containing Al containing Al substrate
2o
3electro-conductive material, the ceramic monolith of surface sputtering metal Al layer, aluminium alloy, surface be coated with in the metal or alloy electro-conductive material of aluminium lamination one or more.
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