CN107805838B - A kind of electrochemical method for synthesizing of out-of-plane orientation phosphate aluminium molecular sieve film - Google Patents
A kind of electrochemical method for synthesizing of out-of-plane orientation phosphate aluminium molecular sieve film Download PDFInfo
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- CN107805838B CN107805838B CN201711005622.3A CN201711005622A CN107805838B CN 107805838 B CN107805838 B CN 107805838B CN 201711005622 A CN201711005622 A CN 201711005622A CN 107805838 B CN107805838 B CN 107805838B
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- molecular sieve
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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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
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Abstract
The invention discloses a kind of electrochemical method for synthesizing of out-of-plane orientation phosphate aluminium molecular sieve film of the synthesis technical field of molecular screen membrane, and specific step is as follows: S1 for the electrochemical method for synthesizing of the out-of-plane orientation phosphate aluminium molecular sieve film: carrying out sanding and polishing to porous stainless steel disc；S2: dry after ultrasonic cleaning；S3: alumina wafer and drying are pressed into；S4: alumina wafer is calcined and is polished flat；S5: cleaning alumina wafer carrier to neutrality；S6: crystal seed liquid preparation；S7: alumina wafer carrier snearing crystal seed liquid；S8: drying is mixed with colloidal sol mixed liquor in drying box；S9: three-electrode system aging；S10: it calcines and molecular screen membrane is made, molecular screen membrane generated time prepared by the present invention is short, form a film uniform and delicate, by adjusting generated time and the easily controllable film forming thickness of voltage, and it is not influenced by hydrothermal condition, it is easy to be made the molecular screen membrane of oriented growth, highly crystalline, its adhesive strength is high, covering is complete, good dispersion.
Description
Technical field
The present invention relates to the synthesis technical field of molecular screen membrane, specially a kind of electrification of out-of-plane orientation phosphate aluminium molecular sieve film
Learn synthetic method.
Background technique
In the synthesis field of molecular sieve, it is most traditional, most simply be also widest synthetic method be hydrothermal synthesis method, be
After having configured molecular screen membrane Synthesis liquid, substrate is directly dipped into Synthesis liquid, under conditions of hydrothermal synthesis, control is suitable
Reaction condition, such as temperature, pressure and generated time directly grow molecular screen membrane in substrate surface.This method and process
Process is simple, does not need to modify carrier in advance, at low cost, and there is no limit so that be conducive to work to the shape of substrate
The production molecular screen membrane of industry batch, but its is maximum the disadvantage is that the molecular screen membrane of synthesis is usually defective, and orientation
Difference, this just brings very big difficulty to the application of molecular screen membrane.Crystal seed method is called secondary growth method, exactly to make up these
Development of defects and come, such methods separate nucleation process and film forming procedure, first pass through the methods of dip-coating, spin coating in substrate
Upper decorating molecule sieves crystal seed, is made into seed layer, then immerses in secondary synthesis liquid the substrate containing seed layer, generally passes through water
Heat treatment makes crystal seed growth film forming, and such methods can greatly reduce the defects count of molecular screen membrane, and by accurately controlling
Core is made and film forming procedure prepares the molecular screen membrane of height-oriented property, but this method and step is more, and wants to crystal seed
Ask high, especially when being synthesized in large area or complicated shape substrate, due to seed layer defect or fall off will lead to and synthesize
Molecular screen membrane existing defects, thus be unfavorable for the large-scale production of molecular screen membrane.For this purpose, we have proposed a kind of out-of-plane orientations
The electrochemical method for synthesizing of phosphate aluminium molecular sieve film comes into operation, to solve the above problems.
Summary of the invention
The purpose of the present invention is to provide a kind of electrochemical method for synthesizing of out-of-plane orientation phosphate aluminium molecular sieve film, on solving
State the problem of proposing in background technique.
To achieve the above object, the invention provides the following technical scheme: a kind of electrification of out-of-plane orientation phosphate aluminium molecular sieve film
Synthetic method is learned, specific step is as follows for the electrochemical method for synthesizing of the out-of-plane orientation phosphate aluminium molecular sieve film:
S1: being polished smooth its surface as carrier, and using sand paper and abrasive pastes using porous stainless steel disc, with removal
The oxide layer on surface；
S2: porous stainless steel disc is cleaned by ultrasonic 20~30min in ultrasonic container using acetone, is then done at room temperature
It is dry spare；
S3: a certain amount of alumina powder and deionized water are stirred evenly, together with the porous stainless steel disc in step S2
It is put into stainless steel mould, alumina wafer is pressed under conditions of certain pressure, and be dried at room temperature for；
S4: dried alumina wafer being put into Muffle furnace and carries out the obtained alumina wafer carrier of temperature programming calcining, and
The alumina wafer carrier calcined is polished flat with sand paper；
S5: alumina wafer then is cleaned with the sodium hydroxide solution of 1mol/L or sodium chloride solution or hydrogen chloride solution and is carried
Body changes carrier surface acid-base property, then with distilled water repeated flushing to neutrality, baking of the alumina wafer carrier at 60 DEG C that treated
It is dry in case, it places spare；
S6: by the molecular sieve mortar grinder of synthesis at tiny powder, molecular sieve powder is then equipped to 5% second
Alcohol suspension, and 15~20min of sonic oscillation is dispersed in ultrasonic cleaning machine, is prepared into crystal seed liquid；
S7: the alumina wafer carrier in step S5 is wanted into the surface of snearing crystal seed downward, level is contacted with crystal seed liquid, 10s
After take out, and the extra crystal seed liquid of alumina wafer carrier edge is sucked out with filter paper；
S8: and then dry 1~1.5d in 60 DEG C of drying box, it is put into glass reaction kettle, and colloidal sol is poured into kettle
Mixed liquor；
S9: being passed through electrode in glass reaction kettle, carries out aging using cyclic voltammetry and potentiostatic method, wherein with oxidation
For aluminium flake carrier as working electrode, the saturated calomel electrode positioned at glass reaction kettle tail portion is distributed in glass as reference electrode
The platinized platinum of reaction kettle end is used as to electrode, using colloidal sol mixed liquor as electrolyte and provides silicon source；
S10: after three-electrode system loads using calcination processing after be made molecular screen membrane.
Preferably, in the step S4, the heating of Muffle furnace internal program is that 20 DEG C of speed with 1 DEG C/min is warming up to 550 DEG C,
And 480~500min is calcined at a high temperature of 550 DEG C, then 20 DEG C are cooled to the speed of 1 DEG C/min.
Preferably, in the step S8, colloidal sol mixed liquor is by acetone, magnesia, aluminium oxide, phosphorus pentoxide and distillation
Water composition, and acetone: magnesia: aluminium oxide: phosphorus pentoxide: distilled water=2:0.2:0.9:1:40.
Preferably, in the step S9, the sweep interval of cyclic voltammetry is -0.2~1.5V, scanning speed 30mV/
S, scanning circle number are 15 circles.
Preferably, in the step S9, the current potential of potentiostatic method is 1.3V, and control electric current is 10mA, decomposition voltage 6V.
Preferably, in the step S10, the temperature of calcining is warming up to 600 DEG C by 20 DEG C of speed with 1 DEG C/min, then
1000~1200 DEG C are warming up to the speed of 1.6 DEG C/min again, calcines 1800~2000min, then persistently with the speed of 1.6 DEG C/min
Degree is cooled to 20 DEG C.
Compared with prior art, the beneficial effects of the present invention are: molecular screen membrane generated time prepared by the present invention is short, forms a film
Uniform and delicate by adjusting generated time and the easily controllable film forming thickness of voltage, and is not influenced by hydrothermal condition, is easy to obtained
The molecular screen membrane of oriented growth, highly crystalline, adhesive strength is high, covering is complete, good dispersion.
Detailed description of the invention
Fig. 1 is work flow diagram of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, carries out to the technical solution in inventive embodiments clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, every other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
Referring to Fig. 1, the present invention provides a kind of technical solution: a kind of electrochemistry formated of out-of-plane orientation phosphate aluminium molecular sieve film
Method, specific step is as follows for the electrochemical method for synthesizing of the out-of-plane orientation phosphate aluminium molecular sieve film:
S1: being polished smooth its surface as carrier, and using sand paper and abrasive pastes using porous stainless steel disc, with removal
The oxide layer on surface；
S2: porous stainless steel disc is cleaned by ultrasonic 20~30min in ultrasonic container using acetone, is then done at room temperature
It is dry spare；
S3: a certain amount of alumina powder and deionized water are stirred evenly, together with the porous stainless steel disc in step S2
It is put into stainless steel mould, alumina wafer is pressed under conditions of certain pressure, and be dried at room temperature for；
S4: dried alumina wafer being put into Muffle furnace and carries out the obtained alumina wafer carrier of temperature programming calcining, and
The alumina wafer carrier calcined is polished flat with sand paper, the heating of Muffle furnace internal program is 20 DEG C of speed liters with 1 DEG C/min
Temperature calcines 480~500min to 550 DEG C at a high temperature of 550 DEG C, is then cooled to 20 DEG C with the speed of 1 DEG C/min；
S5: then with the sodium hydroxide solution of 1mol/L or sodium chloride solution or hydrogen chloride solution
Alumina wafer carrier is cleaned, carrier surface acid-base property is changed, then with distilled water repeated flushing to neutrality, treated
Alumina wafer carrier is dry in 60 DEG C of baking oven, places spare；
S6: by the molecular sieve mortar grinder of synthesis at tiny powder, molecular sieve powder is then equipped to 5% second
Alcohol suspension, and 15~20min of sonic oscillation is dispersed in ultrasonic cleaning machine, is prepared into crystal seed liquid；
S7: the alumina wafer carrier in step S5 is wanted into the surface of snearing crystal seed downward, level is contacted with crystal seed liquid, 10s
After take out, and the extra crystal seed liquid of alumina wafer carrier edge is sucked out with filter paper, colloidal sol mixed liquor is by acetone, magnesia, oxygen
Change aluminium, phosphorus pentoxide and distilled water composition, and acetone: magnesia: aluminium oxide: phosphorus pentoxide: distilled water=2:0.2:
0.9:1:40；
S8: and then dry 1~1.5d in 60 DEG C of drying box, it is put into glass reaction kettle, and colloidal sol is poured into kettle
Mixed liquor；
S9: being passed through electrode in glass reaction kettle, carries out aging using cyclic voltammetry and potentiostatic method, wherein with oxidation
For aluminium flake carrier as working electrode, the saturated calomel electrode positioned at glass reaction kettle tail portion is distributed in glass as reference electrode
The platinized platinum of reaction kettle end is used as to electrode, using colloidal sol mixed liquor as electrolyte and provides silicon source, the scanning of cyclic voltammetry
Section is -0.2~1.5V, scanning speed 30mV/s, and scanning circle number is 15 circles, and the current potential of potentiostatic method is 1.3V, control electricity
Stream is 10mA, decomposition voltage 6V；
S10: after three-electrode system loads using calcination processing after be made molecular screen membrane, the temperature of calcining is by 20
DEG C 600 DEG C are warming up to the speed of 1 DEG C/min, are then warming up to 1000~1200 DEG C again with the speed of 1.6 DEG C/min, persistently forge
1800~2000min is burnt, then is cooled to 20 DEG C with the speed of 1.6 DEG C/min.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. a kind of electrochemical method for synthesizing of out-of-plane orientation phosphate aluminium molecular sieve film, it is characterised in that: the out-of-plane orientation phosphorus aluminium molecule
Specific step is as follows for the electrochemical method for synthesizing of sieve membrane:
S1: its surface is polished smooth as carrier, and using sand paper and abrasive pastes using porous stainless steel disc, to remove surface
Oxide layer；
S2: porous stainless steel disc is cleaned by ultrasonic 20~30min in ultrasonic container using acetone, is then dried at room temperature for standby
With；
S3: a certain amount of alumina powder and deionized water are stirred evenly, and are put into together with the porous stainless steel disc in step S2
In stainless steel mould, alumina wafer is pressed under conditions of certain pressure, and be dried at room temperature for；
S4: dried alumina wafer is put into Muffle furnace and carries out the obtained alumina wafer carrier of temperature programming calcining, and will be forged
Burned alumina wafer carrier is polished flat with sand paper；
S5: then cleaning alumina wafer carrier with the sodium hydroxide solution of 1mol/L or sodium chloride solution or hydrogen chloride solution,
Change carrier surface acid-base property, then with distilled water repeated flushing to neutrality, treated baking oven of the alumina wafer carrier at 60 DEG C
Middle drying is placed spare；
S6: by the molecular sieve mortar grinder of synthesis at tiny powder, then the ethyl alcohol that molecular sieve powder is equipped to 5% is hanged
Turbid, and 15~20min of sonic oscillation is dispersed in ultrasonic cleaning machine, is prepared into crystal seed liquid；
S7: wanting the surface of snearing crystal seed downward for the alumina wafer carrier in step S5, and level is contacted with crystal seed liquid, is taken after 10s
Out, and with filter paper by the extra crystal seed liquid of alumina wafer carrier edge it is sucked out；
S8: and then dry 1~1.5d in 60 DEG C of drying box, it is put into glass reaction kettle, and colloidal sol mixing is poured into kettle
Liquid；
The colloidal sol mixed liquor is made of acetone, magnesia, aluminium oxide, phosphorus pentoxide and distilled water, and acetone: oxidation
Magnesium: aluminium oxide: phosphorus pentoxide: distilled water=2:0.2:0.9:1:40；
S9: being passed through electrode in glass reaction kettle, aging is carried out using cyclic voltammetry and potentiostatic method, wherein with alumina wafer
For carrier as working electrode, the saturated calomel electrode positioned at glass reaction kettle tail portion is distributed in glass reaction as reference electrode
The platinized platinum of kettle end is used as to electrode, using colloidal sol mixed liquor as electrolyte and provides silicon source；
S10: after three-electrode system loads using calcination processing after be made molecular screen membrane.
2. a kind of electrochemical method for synthesizing of out-of-plane orientation phosphate aluminium molecular sieve film according to claim 1, it is characterised in that:
In the step S4, the heating of Muffle furnace internal program is warming up to 550 DEG C for 20 DEG C of speed with 1 DEG C/min, and in 550 DEG C of high temperature
480~500min of lower calcining, is then cooled to 20 DEG C with the speed of 1 DEG C/min.
3. a kind of electrochemical method for synthesizing of out-of-plane orientation phosphate aluminium molecular sieve film according to claim 1, it is characterised in that:
In the step S9, the sweep interval of cyclic voltammetry is -0.2~1.5V, scanning speed 30mV/s, and scanning circle number is 15
Circle.
4. a kind of electrochemical method for synthesizing of out-of-plane orientation phosphate aluminium molecular sieve film according to claim 1,
It is characterized by: the current potential of potentiostatic method is 1.3V in the step S9, control electric current is 10mA,
Decomposition voltage is 6V.
5. a kind of electrochemical method for synthesizing of out-of-plane orientation phosphate aluminium molecular sieve film according to claim 1, it is characterised in that:
In the step S10, the temperature of calcining is warming up to 600 DEG C by 20 DEG C of speed with 1 DEG C/min, then again with 1.6 DEG C/min's
Speed is warming up to 1000~1200 DEG C, persistently calcines 1800~2000min, then be cooled to 20 DEG C with the speed of 1.6 DEG C/min.
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| CN103449475A (en) * | 2012-05-29 | 2013-12-18 | 上海中科高等研究院 | Preparation method of AlPO-18 molecular sieve membrane |
| CN104726889B (en) * | 2013-12-18 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of electrochemical method for synthesizing of phosphate aluminium molecular sieve film |
| CN106673626B (en) * | 2017-01-23 | 2019-12-31 | 郑州玉发精瓷科技有限公司 | Low-cost alumina powder material for producing self-toughening alumina wear-resistant ceramic |
| CN106835245B (en) * | 2017-02-24 | 2018-09-25 | 中国科学院上海高等研究院 | A kind of preparation method of ultra-thin graphene oxide film for molecule screening |
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| Title |
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| Cotemplating Ionothermal Synthesis of a New Open-Framework Aluminophosphate with Unique Al/P Ratio of 6/7;Hongzhu Xing et al.;《Chemical Materials》;20080604;第20卷(第13期);4179–4181 |
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