CN100572600C - Cyclodextrin intercalation hydrotalcite film of vertical substrate grown and preparation method thereof - Google Patents
Cyclodextrin intercalation hydrotalcite film of vertical substrate grown and preparation method thereof Download PDFInfo
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- CN100572600C CN100572600C CNB200810116510XA CN200810116510A CN100572600C CN 100572600 C CN100572600 C CN 100572600C CN B200810116510X A CNB200810116510X A CN B200810116510XA CN 200810116510 A CN200810116510 A CN 200810116510A CN 100572600 C CN100572600 C CN 100572600C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/16—Cyclodextrin; Derivatives thereof
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
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- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
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Abstract
Cyclodextrin intercalation hydrotalcite film of a kind of vertical substrate grown and preparation method thereof belongs to organic-inorganic matrix material and preparing technical field thereof.The chemical formula of intercalated houghite is: [(M
2+)
1-x(M
3+)
x(OH)
2]
X+(CMCD
N-)
X/nMH
2O.The preparation method is earlier with the anodic oxidation of aluminium flake under the constant voltage condition; Take by weighing divalent metal salt more respectively, anion modified cyclodextrin and NH
4NO
3Be dissolved in and be made into the synthetic liquid of reaction in the deionized water, synthesize the pH of liquid between 5.9～8.5 with the ammoniacal liquor conditioned reaction again.Anodised aluminium/aluminium substrate vertically is suspended in the synthetic liquid of above-mentioned reaction, reacts certain hour at a certain temperature and make the cyclodextrin intercalation hydrotalcite film.Advantage is: the cyclodextrin intercalation hydrotalcite film that utilizes in-situ growth technology to obtain is fixed on the aluminium substrate, the immobilization and the device of hydrotalcite have been realized, and the hydrotalcite that obtains has certain mechanical strength, and this will greatly make things convenient for the application of cyclodextrin intercalation hydrotalcite material in productive life.
Description
Affiliated field
The present invention relates to belong to composite organic-inorganic material and preparing technical field thereof, cyclodextrin intercalation hydrotalcite film of a kind of vertical substrate grown and preparation method thereof particularly is provided, has adopted in-situ growth technology to prepare the cyclodextrin intercalation hydrotalcite film material that laminate is arranged perpendicular to the anodic oxidation aluminium substrate.
Background technology
Houghite material (LDHs) is because its unique crystalline structure and physicochemical characteristic make it show very wide application prospect in many fields such as ion-exchange, absorption, catalysis, macromolecule modified, optical material, magnetics material, electricity materials.If houghite is made film,, will widen it greatly in industrial application to realize the device of multi-functional LDHs material.For example: when the catalyzer, not only can improve its service efficiency to hydrotalcite film, and can solve problems such as the separating of catalyzer and reactant, catalyst loss, recovery because of improving surface-area.When as the electrode modification material, can improve electrode performance well.Therefore, this class material is made film, still all have very high value in actual applications in fundamental research.
At document (1) J.Am.Chem.Soc., 2006, among the 128:4872-4880, people such as Takayoshi Sasaki are at first with Co-Al hydrotalcite stripping layer, obtained the hydrotalcite film that hydrotalcite laminate and anion superpolymer are alternately arranged with the layer assembly method then, for the preparation hydrotalcite film provides novel method.
At document (2) Adv.Mater., 2006, among the 18:3089-3093, Duan Xue etc. adopt the original position synthetic technology, with the aluminium flake after surperficial anodic oxidation is substrate, utilize the anodised aluminium on the substrate surface to provide the hydrotalcite growth required aluminium source, the pH value by dropping ammonia conditioned reaction solution makes Ni in the solution
2+Ion and NH
3Near nickel aluminium nitrate radical hydrotalcite (NiAl-LDHs) film that grows the controlled vertical substrate growth of density under the neutrallty condition, and find that this film has super-hydrophobic performance.
At document (3) Chem.Mater., 2004, among the 16:3774-3779, employing solvent evaporation technology such as Duk-Young Jung be substrate preparation with silicon single crystal laminate be parallel to the hydrotalcite film that the substrate direction is arranged.The author thinks the changing conditions that can obviously make things convenient for research hydrotalcite pattern and interlamellar spacing in ion exchange reaction after the hydrotalcite film forming.
Cyclodextrin (cyclodextrin, CD) be by α-1 by α-D-glucopyranose unit, the member cyclic oligosaccharides that the 4-glycosidic link is formed, because cyclodextrin and derivative thereof have special chiral ring cavity, good chiral environment can be provided, they not only are widely used in the separating optical isomeric body, also are used to separate various geometrical isomers.Cyclodextrin is inserted hydrotalcite layers as guest molecule, can realize the immobilization of cyclodextrin, for the magnanimity chiral separation provides possibility.If can prepare cyclodextrin intercalation hydrotalcite film, with the application that greatly makes things convenient for it in productive life.The expection cyclodextrin intercalation hydrotalcite film is in chiral separation, and fields such as chiral material inclusion have very high potential using value.The cyclodextrin intercalation hydrotalcite film that vertical substrate is arranged about laminate yet there are no report at present.
Summary of the invention
Cyclodextrin intercalation hydrotalcite film that provides a kind of vertical substrate grown and preparation method thereof is provided the object of the invention.Utilize the in-situ growth technology of hydrotalcite, synthesize cyclodextrin intercalation hydrotalcite film in anodic oxidation aluminium substrate previous step, but the method for modulation laminate species of metal ion, the substituent type that changes cyclodextrin and substitution value prepares the cyclodextrin intercalation hydrotalcite film matrix material that the vertical substrate of a series of laminates is arranged simultaneously.
Cyclodextrin intercalation hydrotalcite film of the present invention is a supramolecular structure, and its crystalline structure is the crystalline structure of houghite material, and its chemical formula is:
[(M
2+)
1-x(M
3+)
x(OH)
2]
x+(CD
n-)
x/n·mH
2O，
0.2≤x≤0.33 wherein, n=0.5-14, m=3-6 are interlayer crystal water molecule number,
M
2+Representing divalent-metal ion, can be Ni
2+, Zn
2+, Co
2+, Fe
2+, Ca
2+, Mn
2+, Cu
2+Any, M
2+Preferred Zn
2+, Ni
2+, Co
2+
M
3+Represent Al
3+Ion.
The preparation process of cyclodextrin intercalation hydrotalcite film of the present invention is as follows:
A. aluminium flake is cleaned 2～10min in dehydrated alcohol and deionized water for ultrasonic, put into NaOH solution then and handle 1～3min, rinse well with deionized water again.As anode, lead flake is as negative electrode, with H with the aluminium flake after cleaning
2SO
4Solution is made electrolytic solution, the constant voltage oxidation.Operating voltage 15～25V, oxidation current are 1.5～3A, and electrolysis time is 0.5～2h, and electrolysis temperature is a room temperature, make the surface of metallic aluminium form anodic aluminum oxide layer.25～90 ℃ of dry backs are standby.
B. take by weighing divalent metal salt respectively, anion modified cyclodextrin and NH
4NO
3Be dissolved in and be made into the synthetic liquid of reaction in the deionized water, synthesize the pH of liquid between 5.9～8.5 with the ammoniacal liquor conditioned reaction again.Anodised aluminium/aluminium (AAO/Al) substrate vertically is suspended in the synthetic liquid of above-mentioned reaction, under 40～130 ℃ of temperature, reacts 12～96h., dry under room temperature behind deionized water rinsing 3～5 times after reaction finishes with after the sample taking-up, obtain cyclodextrin intercalation hydrotalcite film.
Divalent metal salt of the present invention is selected divalent metal Ni
2+, Zn
2+, Co
2+, Fe
2+, Ca
2+, Mn
2+, Cu
2+In any and anion N O
3 -, Cl
-, Br
-, I
-In any combination.
Above-mentioned materials is carried out XRD, IR, scanning electron microscope to be characterized and shows and successfully prepared cyclodextrin intercalated hydrotalcite film.By the XRD structural parameter as can be known cyclodextrin take the monolayer alignment mode of axis normal laminate in hydrotalcite layers, and its unit cell parameters a value is close with the cyclodextrin intercalation hydrotalcite powder, shows that product has complete laminate structure.As can be seen, in the cyclodextrin intercalation hydrotalcite film for preparing, the hydrotalcite laminate is perpendicular to substrate, and arrangement is fine and close from stereoscan photograph.Discover that further this cyclodextrin intercalation hydrotalcite film has the function of chiral separation racemic modification, for the preparation of the magnanimity of chiral material provides a new way.
The invention has the advantages that: utilize in-situ growth technology, the cyclodextrin with chiral separation performance can be assembled into hydrotalcite layers, realize the immobilization of cyclodextrin and the device of hydrotalcite material.Studies confirm that this film has the ability of chiral separation racemic modification.Simultaneously can also pass through the substituent type of modulation cyclodextrin, substitution value and divalent-metal ion kind prepare a series of cyclodextrin intercalation hydrotalcite film materials.Adopt the reactive force of the hydrotalcite film of this method preparation and substrate stronger, difficult drop-off.
Description of drawings
Fig. 1 is the anodic oxidation aluminium substrate of embodiment 1 preparation and the X-ray powder diffraction figure of carboxymethyl-beta-cyclodextrin intercalated hydrotalcite film.
Fig. 2 is the scanning electron microscope vertical view of embodiment 1 carboxymethyl-beta-cyclodextrin intercalated hydrotalcite film.
Fig. 3 is the scanning electron microscope sectional view of embodiment 1 carboxymethyl-beta-cyclodextrin intercalated hydrotalcite film.
Embodiment:
Embodiment 1
Steps A: aluminium flake is cut into the sheet of 10cm * 10cm, clean 3min, put into the NaOH solution of 0.1M then and handle 2min, rinse well with deionized water again in dehydrated alcohol and deionized water for ultrasonic.As anode, lead flake is as negative electrode, with the H of 1M with the aluminium flake after cleaning
2SO
4Solution is made electrolytic solution, the constant voltage oxidation.Operating voltage 20V, the about 100cm of oxidation area of aluminium flake
2, oxidation current is 2A, and electrolysis time is 1h, and electrolysis temperature is a room temperature, makes the surface of metallic aluminium form anodic aluminum oxide layer.In the oxidising process, small bubbles (H is arranged constantly on the lead flake
2) produce, the dry rear surface of the aluminium flake after the surperficial anodic oxidation is white in color and (is Al
2O
3The color of rete).Sample is clean with a large amount of washed with de-ionized water, and 70 ℃ of dry backs are standby.
Step B: take by weighing 2.908g Ni (NO respectively
3)
26H
2O (0.1mol), 0.5g carboxymethyl cyclodextrin (substitution value 4.1) and 4.8g NH
4NO
3(0.6mol) be dissolved in and be made into the synthetic liquid of 100ml reaction in the deionized water, use the NH of concentration 1% again
3H
2The pH of the synthetic liquid of O conditioned reaction is 6.8.With size is that 1cm * 2cm anodised aluminium/aluminium (AAO/Al) substrate vertically is suspended in the synthetic liquid of above-mentioned reaction, reacts 48h down at 75 ℃., dry under room temperature behind deionized water rinsing after reaction finishes with after the sample taking-up, obtain cyclodextrin intercalation hydrotalcite film.
By X-ray diffractogram as can be known, adopt the cyclodextrin intercalation hydrotalcite film of growth in situ method preparation, carboxymethyl-beta-cyclodextrin enters the hydrotalcite film interlayer, and its laminate spacing is 1.844nm; The cyclodextrin that intercalation is described is taked the monolayer alignment mode of axis normal substrate at interlayer.As can be seen in this film, the hydrotalcite laminate is the arrangement mode perpendicular to substrate from the plane of scanning electron microscope and cross-section photograph, and the thickness of film is approximately 0.5 μ m.
Embodiment 2
Steps A: obtain the AAO/Al substrate by steps A method among the embodiment 1.
Step B: take by weighing 2.974g Zn (NO respectively
3)
26H
2O (0.1mol), 0.5g carboxymethyl cyclodextrin (substitution value 4.1) and 4.8g NH
4NO
3(0.6mol) be dissolved in and be made into the synthetic liquid of 100ml reaction in the deionized water, use the NH of concentration 1% again
3H
2The pH of the synthetic liquid of O conditioned reaction is 6.5.With size is that 1cm * 2cm anodised aluminium/aluminium (AAO/Al) substrate vertically is suspended in the synthetic liquid of above-mentioned reaction, reacts 48h down at 75 ℃., dry under room temperature behind deionized water rinsing after reaction finishes with after the sample taking-up, obtain cyclodextrin intercalation hydrotalcite film.
By X-ray diffractogram as can be known, adopt the cyclodextrin intercalation hydrotalcite of growth in situ method preparation, carboxymethyl-beta-cyclodextrin can enter the hydrotalcite film interlayer, and its laminate spacing is 1.857nm; The cyclodextrin that intercalation is described is taked the monolayer alignment mode of axis normal substrate at interlayer.As can be seen in this film, the hydrotalcite laminate is the arrangement mode perpendicular to substrate from the plane of scanning electron microscope and cross-section photograph, and the thickness of film is approximately 0.5 μ m.
Embodiment 3
Steps A: obtain the AAO/Al substrate by steps A method among the embodiment 1.
Step B: take by weighing 2.932g Co (NO respectively
3)
26H
2O (0.1mol), 0.5g carboxymethyl cyclodextrin (substitution value 4.1) and 4.8g NH
4NO
3(0.6mol) be dissolved in and be made into the synthetic liquid of 100ml reaction in the deionized water, use the NH of concentration 1% again
3H
2The pH of the synthetic liquid of O conditioned reaction is 6.5.With size is that 1cm * 2cm anodised aluminium/aluminium (AAO/Al) substrate vertically is suspended in the synthetic liquid of above-mentioned reaction, reacts 48h down at 75 ℃., dry under room temperature behind deionized water rinsing after reaction finishes with after the sample taking-up, obtain cyclodextrin intercalation hydrotalcite film.
By X-ray diffractogram as can be known, adopt the cyclodextrin intercalation hydrotalcite of growth in situ method preparation, carboxymethyl-beta-cyclodextrin enters the hydrotalcite film interlayer through ion-exchange, and its laminate spacing is 1.846nm; The cyclodextrin that intercalation is described is taked the monolayer alignment mode of axis normal substrate at interlayer.As can be seen in this film, the hydrotalcite laminate is the arrangement mode perpendicular to substrate from the plane of scanning electron microscope and cross-section photograph, and the thickness of film is approximately 0.5 μ m.
Embodiment 4
Steps A: obtain the AAO/Al substrate by steps A method among the embodiment 1.
Step B: take by weighing 2.908g Ni (NO respectively
3)
26H
2O (0.1mol), 0.5g sulfonic group cyclodextrin (substitution value 6.0) and 4.8g NH
4NO
3(0.6mol) be dissolved in and be made into the synthetic liquid of 100ml reaction in the deionized water, use the NH of concentration 1% again
3H
2The pH of the synthetic liquid of O conditioned reaction is 6.5.With size is that 1cm * 2cm anodised aluminium/aluminium (AAO/Al) substrate vertically is suspended in the synthetic liquid of above-mentioned reaction, reacts 48h down at 75 ℃., dry under room temperature behind deionized water rinsing after reaction finishes with after the sample taking-up, obtain cyclodextrin intercalation hydrotalcite film.
By X-ray diffractogram as can be known, adopt the cyclodextrin intercalation hydrotalcite of growth in situ method preparation, the sulfonic acid group-beta-cyclodextrin enters the hydrotalcite film interlayer through ion-exchange, and its laminate spacing is 1.832nm; The cyclodextrin that intercalation is described is taked the monolayer alignment mode of axis normal substrate at interlayer.As can be seen in this film, the hydrotalcite laminate is the arrangement mode perpendicular to substrate from the plane of scanning electron microscope and cross-section photograph, and the thickness of film is approximately 0.5 μ m.
Claims (1)
1, a kind of preparation method of cyclodextrin intercalation hydrotalcite film of vertical substrate grown is characterized in that: preparation technology is:
A. aluminium flake is cleaned 2～10min in dehydrated alcohol and deionized water for ultrasonic, put into NaOH solution then and handle 1～3min, rinse well with deionized water again; As anode, lead flake is as negative electrode, with H with the aluminium flake after cleaning
2SO
4Solution is made electrolytic solution, the constant voltage oxidation; Operating voltage 15～25V, oxidation current are 1.5～3A, and electrolysis time is 0.5～2h, and electrolysis temperature is a room temperature, make the surface of metallic aluminium form anodic aluminum oxide layer; 25～90 ℃ of dry backs are standby;
B. take by weighing divalent metal salt respectively, anion modified cyclodextrin and NH
4NO
3Be dissolved in and be made into the synthetic liquid of reaction in the deionized water, synthesize the pH of liquid between 5.9～8.5 with the ammoniacal liquor conditioned reaction again; Anodised aluminium/aluminium substrate vertically is suspended in the synthetic liquid of above-mentioned reaction, under 40～130 ℃ of temperature, reacts 12～96h; After reaction finishes sample is taken out, dry under room temperature behind deionized water rinsing 3～5 times, obtain cyclodextrin intercalation hydrotalcite film;
Described cyclodextrin intercalation hydrotalcite film is to be substrate and aluminium source with the anodised aluminium, and the cyclodextrin intercalation hydrotalcite laminate is perpendicular to the substrate structure arranged; Chemical formula is: [(M
2+)
1-x(M
3+)
x(OH)
2]
X+(CD
N-)
X/nMH
2O, 0.2≤x≤0.33 wherein, n=0.5-14, m=3-6 are interlayer crystal water molecule number, M
2+Be divalent-metal ion Ni
2+, Zn
2+, Co
2+, Fe
2+, Ca
2+, Mn
2+, Cu
2+Any, M
3+Represent trivalent metal ion Al
3+CD represents the cyclodextrin that carboxymethyl or sulfonic group are modified.
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|---|---|---|---|
| CNB200810116510XA CN100572600C (en) | 2008-07-11 | 2008-07-11 | Cyclodextrin intercalation hydrotalcite film of vertical substrate grown and preparation method thereof |
| PCT/CN2009/072076 WO2010003336A1 (en) | 2008-07-11 | 2009-06-01 | A cyclodextrin intercalated hydrotalcite thin-film vertically grown on a substrate, and a method for producing the same |
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|---|---|---|---|
| CNB200810116510XA CN100572600C (en) | 2008-07-11 | 2008-07-11 | Cyclodextrin intercalation hydrotalcite film of vertical substrate grown and preparation method thereof |
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| CN100572600C (en) * | 2008-07-11 | 2009-12-23 | 北京化工大学 | Cyclodextrin intercalation hydrotalcite film of vertical substrate grown and preparation method thereof |
| CN101530620B (en) * | 2009-03-18 | 2012-05-23 | 北京化工大学 | Triphosadenine intercalated houghite membrane and preparation method thereof |
| CN102776536B (en) * | 2011-05-12 | 2014-10-22 | 中国科学院合肥物质科学研究院 | Mercapto-beta-cyclodextrin modified silver nano-rode array, its preparation method and its use |
| ITMI20120009A1 (en) | 2012-01-04 | 2013-07-05 | F B Balzanelli Avvolgitori S P A | PROCEDURE AND EQUIPMENT FOR WINDING PIPES INTO COIL AND FOR PACKAGING THE FORMED COIL |
| CN102650065B (en) * | 2012-05-08 | 2014-09-10 | 淄博职业学院 | Calixarene intercalated hydrotalcite film for in-situ growth on aluminum substrate and preparation method for film |
| CN104058469B (en) * | 2014-07-10 | 2015-06-10 | 淄博职业学院 | Carboxymethyl-beta-cyclodextrin polymer intercalated hydrotalcite material and preparation method thereof |
| CN106633215B (en) * | 2016-10-24 | 2019-04-09 | 北京师范大学 | Sulfonated β-cyclodextrin-LDH complex and its synthetic method |
| CN108034988B (en) * | 2017-12-08 | 2019-09-06 | 山东理工大学 | Using porous anodic alumina template as three-dimensional hydrotalcite film of substrate and preparation method thereof |
| CN107913723B (en) * | 2017-12-08 | 2020-06-23 | 山东理工大学 | Chromium-containing three-dimensional nickel-aluminum hydrotalcite-like film and preparation method and application thereof |
| CN109023299A (en) * | 2018-07-31 | 2018-12-18 | 山东科技大学 | A kind of preparation method of the hydrotalcite of magnesium/magnesium alloy-alumina composite coating |
| CN109735831A (en) * | 2019-03-12 | 2019-05-10 | 姜水英 | A method of in aluminum alloy surface chemical plating stannum-intercalation corrosion inhibiter ion-laser melting coating |
| CN111135798B (en) * | 2020-01-09 | 2022-04-08 | 常熟理工学院 | Rust material and preparation method and application thereof |
| CN112808318B (en) * | 2020-12-24 | 2022-05-17 | 中国矿业大学(北京) | Catalyst for preparing anisole from phenol and dimethyl carbonate |
| CN113150440B (en) * | 2021-04-12 | 2022-08-26 | 浙江理工大学 | Preparation method of flame-retardant polypropylene |
| CN113304776B (en) * | 2021-05-24 | 2023-09-05 | 郑州轻工业大学 | Preparation method of dipropylene glycol and catalyst thereof |
| CN113104872B (en) * | 2021-05-24 | 2022-10-21 | 北京化工大学 | Method for preparing organic molecule intercalation hydrotalcite array by one-step method |
| CN115738757B (en) * | 2022-11-24 | 2024-03-29 | 中国海洋大学 | Monovalent cation selective separation membrane based on sulfobutyl-beta-cyclodextrin ion transmission channel, and preparation method and application thereof |
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| CN1830799A (en) * | 2006-02-28 | 2006-09-13 | 北京化工大学 | Carboxymethyl-beta-cyclodextrin intercalated water talc used for chiral resolution racemic modification and its preparation method |
| CN100572600C (en) * | 2008-07-11 | 2009-12-23 | 北京化工大学 | Cyclodextrin intercalation hydrotalcite film of vertical substrate grown and preparation method thereof |
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| 磺化环糊精插层结构水滑石的制备及其对手性物质选择性吸附的初步研究. 王继.中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑，第1期. 2005 |
| 磺化环糊精插层结构水滑石的制备及其对手性物质选择性吸附的初步研究. 王继.中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑，第1期. 2005 * |
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