CN100427401C - Preparation method of highly oriented transparent dihydroxy metal oxide film - Google Patents

Preparation method of highly oriented transparent dihydroxy metal oxide film Download PDF

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CN100427401C
CN100427401C CNB2005101307817A CN200510130781A CN100427401C CN 100427401 C CN100427401 C CN 100427401C CN B2005101307817 A CNB2005101307817 A CN B2005101307817A CN 200510130781 A CN200510130781 A CN 200510130781A CN 100427401 C CN100427401 C CN 100427401C
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ldhs
film
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CN1800028A (en
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王连英
刘淼
段雪
李仓
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/04—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides

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  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention provides a preparation method for high orientation transparent di-hydroxyl composite metal oxide thin films, which belongs to the technical field of di-hydroxyl composite metal oxide. LDHs nanometer particles in a sheet-shaped structure are prepared by a nucleation/crystallization isolation method, the particle size distribution of the LDHs nanometer particles is uniform, solvents are directly evaporated by a solvent evaporating method to form continuous high orientation transparent LDHs thin films by using the sheet-shaped structure of the LDHs nanometer particles, and the multifunctional LDHs thin films can be prepared by the control and the regulation of the varieties and the composition of metallic elements of main body laminated plates and interlaminar object anions. The present invention has the advantages of simple device requirement and easy operation, the prepared high orientation transparent LDHs thin films overcome the limitation of LDHs powder materials in practical use, and the application in the aspects of photoelectrocatalysis, separation, sensors, etc. becomes possible.

Description

A kind of preparation method of highly oriented transparent dihydroxy metal oxide film
Affiliated field
The invention belongs to the di-hydroxyl composite metal oxidate technical field, be specifically related to a kind of preparation method of highly oriented transparent dihydroxy metal oxide film.
Background technology
It is a kind of anionic type laminated material that layered di-hydroxyl composite metal oxidate is called hydrotalcite (Layered Double Hydroxides is abbreviated as LDHs) again.LDHs main body laminate chemical constitution, interlayer anion kind and quantity etc. all have Modulatory character, thereby have multiple physicochemical property, are with a wide range of applications at aspects such as catalysis, separation, transmitter, photochemistry, electrochemistry.At present, research and application to LDHs both at home and abroad generally all is confined to the LDHs powder body material, yet the LDHs powder body material exists shortcomings such as easy loss, recovery difficulty, LDHs is made the highly oriented transparent film then can overcome above-mentioned shortcoming, simultaneously can reduce reflection of light and scattering loss, make its application become possibility at aspects such as photoelectrocatalysis, separation and transmitters.
The method for preparing the LDHs film of bibliographical information has following two kinds at present: Langmuir-Blodgett method (LB method) and laminate are peeled off construction from part.
Document [J.X.He, K.Kobayashi, M.Takahashi, G.Villemure, A.Yamagishi, Thin SolidFilms, 2001,397,255] adopt the LB method, individual layer anionic amphiphilic Ru (II) title complex is adsorbed LDHs as template, prepare metal complexes/LDHs composite membrane.But the LDHs film that this method is made is the ultrathin membrane of nanometer grade thickness, and is difficult to obtain large-area continuous film by this method, therefore only is confined to the fundamental research of microscopic fields such as molecular electronic device, simulation microbial film.
Document [L.Li, R.Ma, Y.Ebina, N.Iyi, T.Sasaki, Chem.Mater., 2005,17,4386] adopt laminate to peel off construction from part, by electrostatic forcing with the LDHs laminate peeled off and polyanion electrolyte alternating deposit on electronegative substrate, prepare LDHs/ polyelectrolyte nano thin-film.The shortcoming of this method is that laminate stripping process complexity is wayward, laminate after peeling off active high, easily assemble, and the function of the LDHs film of preparing with this method at present is subjected to the restriction of interlayer anion kind.
Summary of the invention
The objective of the invention is to: provide a kind of preparation method-solvent evaporated method of highly oriented transparent dihydroxy metal oxide film, the preparation highly oriented transparent dihydroxy metal oxide film.The LDHs film of this method preparation has overcome LDHs powder body material limitation in actual applications, makes its application at aspects such as photoelectrocatalysis, separation and transmitters become possibility.
The present invention utilizes solvent evaporated method to prepare highly oriented transparent LDHs film.Adopt nucleation/crystallization isolation method to prepare nano-scale, the uniform sheet inorganic anion of size distribution intercalation LDHs; The anion intercalated LDHs of organic anion and title complex prepares by organic anion or title complex negatively charged ion and resulting inorganic anion intercalation LDHs are carried out ion-exchange.Above-mentioned LDHs nanoparticle is mixed with certain density suspension, and evaporating solvent can obtain highly oriented transparent LDHs film.The concrete operations step is as follows:
The preparation of A.LDHs nanoparticle: adopt patent (seeing patent application 00132145.5) method to prepare the inorganic anion intercalation LDHs of required nano-scale sheet structure, wherein the concentration of mixed metal salt is 0.4～2.1M, laminate divalence, trivalent metal cation mol ratio (M 2+/ M 3+) be 2～4: 1, divalent metal M 2+Can be Mg 2+, Ni 2+, Zn 2+, Fe 2+Or Cu 2+In a kind of, trivalent metal cation M 3+Can be Al 3+, Fe 3+, Co 3+, Ti 3+Or Ga 3+In a kind of.Or the employing ion exchange method, organic anion or title complex negatively charged ion and above-mentioned inorganic anion intercalation LDHs are carried out ion-exchange, generating interlayer is the anion intercalated LDHs nanoparticle of organic anion or title complex.
Inorganic anion is Cl -, NO 3 -, CO 3 2-, SO 4 2-Deng the inorganic acid radical negatively charged ion, organic anion is organic acid negatively charged ion such as hexanodioic acid root, malonate, terephthaldehyde's acid group, salicylate, and the title complex negatively charged ion is Tb (EDTA) -(EDTA=ethylenediamine tetraacetic acid (EDTA) root), Zn (BPS) 3 4-(BPS=4,7-phenylbenzene-1,10-phenanthroline disulfonic acid root), Fe (CN) 6 3-Deng.
B. the preparation of highly oriented transparent LDHs film: adopt solvent evaporated method to prepare highly oriented transparent LDHs film.The LDHs nanoparticle is dispersed in CO 2Water in, the preparation obtain the suspension that concentration is 0～0.4g/mL, at 20～80 ℃ of following direct evaporation solvents, can obtain highly oriented transparent LDHs film.
LDHs film LDHs main body laminate divalent metal M of the present invention 2+Be Mg 2+, Ni 2+, Zn 2+, Fe 2+Or Cu 2+In a kind of, trivalent metal cation M 3+Be Al 3+, Fe 3+, Co 3+, Ti 3+Or Ga 3+In a kind of.LDHs main body laminate divalent metal M 2+Preferred Mg 2+, Ni 2+Or Zn 2+In a kind of; Trivalent metal cation M 3+Preferred Al 3+Or Fe 3+In a kind of.The LDHs interlayer anion can be Cl -, NO 3 -, CO 3 2-, SO 4 2-Deng the inorganic acid radical negatively charged ion, organic acid negatively charged ion or Tb (EDTA) such as hexanodioic acid root, malonate, terephthaldehyde's acid group, salicylate -(EDTA=ethylenediamine tetraacetic acid (EDTA) root), Zn (BPS) 3 4-(BPS=4,7-phenylbenzene-1,10-phenanthroline disulfonic acid root), Fe (CN) 6 3-Deng the title complex negatively charged ion
Above-mentioned materials is carried out this method of XRD, SEM sign proof successfully prepare highly oriented transparent LDHs film.The XRD spectra of LDHs film and the XRD spectra of corresponding LDHs powder of the same race are contrasted as can be known, in the XRD spectra of LDHs film only at low angle tangible LDHs (00l) characteristic diffraction peak appears, and the characteristic diffraction peak of its h, k ≠ 0 disappears, and shows that the particle of LDHs film is orientated along the c direction of principal axis.The SEM photo shows that the LDHs film surface is smooth, and most particles are the tiling attitude, and the section place can be observed tangible laminate structure.
The LDHs nanoparticle that adopts nucleation/crystallization isolation method to prepare is a sheet structure, and size distribution is even.In deposition process, LDHs nanoparticle trend is arranged in the minimum mode of energy, promptly arranges perpendicular to the mode of substrate with the c axle of LDHs structure cell, thereby forms along the LDHs film of c direction of principal axis orientation.Utilize the interchangeability of LDHs interlayer anion simultaneously, behind organic anion or title complex negatively charged ion introducing interlayer, the LDHs nano particle diameter distributes and does not change, and therefore can form equally along the LDHs film of c direction of principal axis orientation.Because the c axle orientations of LDHs nanoparticle has reduced reflection of light and scattering loss in the film, therefore the LDHs film of preparation shows the transparency.
The invention has the advantages that: the LDHs film of preparing has high orientation, transparent and big area (can reach centimetre-sized) is continuous; Can regulate and control the kind and the composition of LDHs laminate metallic element and interlayer anion as required, obtain multi-functional LDHs film; Equipment requirements is simple, processing ease, is expected to realize the suitability for industrialized production of LDHs film.
Embodiment
Embodiment 1
Steps A: take by weighing 41.03g Mg (NO 3) 26H 2O and 30.01g Al (NO 3) 39H 2O is dissolved in 300mL and removes CO 2In the water, be mixed with mixing salt solution, other gets 19.2g NaOH and is dissolved in 300mL and removes CO 2In the water, rapidly alkaline solution and mixing salt solution are poured under the room temperature in the full back-mixing rotation liquid film reactor and reacted 1min, the gained slurries are at 100 ℃, N 2Protection is crystallization 8h down, and centrifugation is extremely neutral with the sample washing that obtains.After taking out 60 ℃ of following dry 24h of small amount of sample and grinding, obtain Mg 2Al-NO 3The LDHs powder.
Step B: take by weighing the sample behind the 1.5g centrifuge washing, add 10mL and remove CO 2Stir under the water, room temperature, pour in the culture dish, dry 4h under 60 ℃ can obtain transparent Mg 2Al-NO 3The LDHs film, its Mg 2+/ Al 3+=2.
With Mg 2Al-NO 3The XRD spectra of LDHs film and Mg 2Al-NO 3The XRD spectra of LDHs powder contrasts as can be known, Mg 2Al-NO 3Only tangible LDHs (003) and (006) characteristic diffraction peak occur in the XRD spectra of LDHs film, and the characteristic diffraction peak of its (012), (015), (110) and (113) (h, k ≠ 0) disappears, and shows Mg at low angle 2Al-NO 3The particle of LDHs film is orientated along the c direction of principal axis.The SEM photo shows Mg 2Al-NO 3The LDHs film surface is smooth, and most particles are the tiling attitude, and the section place can be observed tangible laminate structure, and thickness is 20 μ m.
Embodiment 2
Steps A: take by weighing 38.68g Nii (NO 3) 26H 2O and 24.99g Al (NO 3) 39H 2O is dissolved in 250mL and removes CO 2Water in, be mixed with mixing salt solution, other gets 15.20g NaOH and is dissolved in 250mL and removes CO 2Water in, rapidly alkaline solution and mixing salt solution are poured under the room temperature in the full back-mixing rotation liquid film reactor and are reacted 1min, the gained slurries are at 100 ℃, N 2Protection is crystallization 8h down, and centrifugation is extremely neutral with the sample washing that obtains.After taking out 60 ℃ of following dry 24h of small amount of sample and grinding, obtain Ni 2Al-NO 3The LDHs powder.
Step B: take by weighing the sample behind the 3g centrifuge washing, add 10mL and remove CO 2Stir under the water, room temperature, pour in the culture dish, dry 4d under 20 ℃ can obtain green transparent Ni 2Al-NO 3The LDHs film, its Ni 2+/ Al 3+=2.
With Ni 2Al-NO 3The XRD spectra of LDHs film and Ni 2Al-NO 3The XRD spectra of LDHs powder contrasts as can be known, Ni 2Al-NO 3Only tangible LDHs (003) and (006) characteristic diffraction peak occur in the XRD spectra of LDHs film, and the characteristic diffraction peak of its (012), (015), (110) and (113) (h, k ≠ 0) disappears, and shows Ni at low angle 2Al-NO 3The particle of LDHs film is orientated along the c direction of principal axis.The SEM photo shows Ni 2Al-NO 3The LDHs film surface is smooth, and most particles are the tiling attitude, and the section place can be observed tangible laminate structure, and thickness is 40 μ m.
Embodiment 3
Steps A: take by weighing 28.56g Zn (NO 3) 26H 2O and 9.00g Al (NO 3) 39H 2O is dissolved in 150mL and removes CO 2Water in, be mixed with mixing salt solution, other gets 9.12g NaOH and is dissolved in 150mL and removes CO 2Water in, rapidly alkaline solution and mixing salt solution are poured under the room temperature in the full back-mixing rotation liquid film reactor and are reacted 1min, the gained slurries are at 100 ℃, N 2Protection is crystallization 8h down, and centrifugation is extremely neutral with the sample washing that obtains.After taking out 60 ℃ of following dry 24h of small amount of sample and grinding, obtain Zn 2Al-NO 3The LDHs powder.
Step B: take by weighing the sample behind the 2g centrifuge washing, add 10mL and remove CO 2Stir under the water, room temperature, pour in the culture dish, dry 6h under 50 ℃ can obtain transparent Zn 2Al-NO 3The LDHs film, its Zn 2+/ Al 3+=2.
With Zn 2Al-NO 3The XRD spectra of LDHs film and Zn 2Al-NO 3The XRD spectra of LDHs powder contrasts as can be known, Zn 2Al-NO 3Only tangible LDHs (003), (006) and (009) characteristic diffraction peak occur in the XRD spectra of LDHs film, and the characteristic diffraction peak of its (012), (015), (110) and (113) (h, k ≠ 0) disappears, and shows Zn at low angle 2Al-NO 3The particle of LDHs film is orientated along the c direction of principal axis.The SEM photo shows Zn 2Al-NO 3The LDHs film surface is smooth, and most particles are the tiling attitude, and the section place can be observed tangible laminate structure, and thickness is 30 μ m.
Embodiment 4
Steps A: the method by steps A among the embodiment 3 obtains Zn 2Al-NO 3LDHs.
Step B: take by weighing 6.63g Zn 2Al-NO 3LDHs (water ratio is 73%) is scattered in 50mL and removes CO 2Make suspension in the water.Take by weighing 3.20g sodium salicylate (C 7H 5NaO 3), be dissolved in 200mL and remove CO 2In the water.LDHs suspension and sodium salicylate solution are poured in the four-hole bottle, are regulated pH=7, under 70 ℃, N 2 protections, carry out ion-exchange 8h with NaOH solution, centrifugation, with the sample washing that obtains to neutral.After taking out 60 ℃ of following dry 24h of small amount of sample and grinding, obtain Zn 2Al-C 7H 5O 3The LDHs powder.
Step C: take by weighing the sample behind the 1g centrifuge washing, add 10mL and remove CO 2Stir under the water, room temperature, pour in the culture dish, dry 3h under 70 ℃ can obtain transparent Zn 2Al-C 7H 5O 3The LDHs film.
With Zn 2Al-C 7H 5O 3The XRD spectra of LDHs film and Zn 2Al-C 7H 5O 3The XRD spectra of LDHs powder contrasts as can be known, Zn 2Al-C 7H 5O 3Only tangible LDHs (003), (006), (009) and (0012) characteristic diffraction peak occur in the XRD spectra of LDHs film, and the characteristic diffraction peak of its (012), (015), (110) and (113) (h, k ≠ 0) disappears, and shows Zn at low angle 2Al-C 7H 5O 3The particle of LDHs film is orientated along the c direction of principal axis.The SEM photo shows Zn 2Al-C 7H 5O 3The LDHs film surface is smooth, and most particles are the tiling attitude, and the section place can be observed tangible laminate structure, and thickness is 20 μ m.
Embodiment 5
Steps A: the method by steps A among the embodiment 3 obtains Zn 2Al-NO 3LDHs.
Step B: take by weighing 37.40gTb respectively 4O 7With 58.4g ethylenediamine tetraacetic acid (EDTA) (H 4EDTA) in there-necked flask, add 500mL deionized water post-heating backflow 24h, regulate pH=6 with 0.5M NaOH, obtain the Na[Tb that concentration is 0.4mol/L (EDTA) behind the suction filtration] solution.
Step C: measure 120mLNa[Tb (EDTA)] solution, pour in the four-hole bottle, add 7.8g Zn again 2Al-NO 3LDHs (water ratio is 73%).Regulate pH=6 with NaOH solution, at 70 ℃, N 2Protection is carried out ion-exchange 24h down, and centrifugation is extremely neutral with the sample washing that obtains.After taking out 60 ℃ of following dry 24h of small amount of sample and grinding, obtain Zn 2Al-TbEDTA LDHs powder.
Step D: take by weighing the sample behind the 3.5g centrifuge washing, add 10mL and remove CO 2Stir under the water, room temperature, pour in the culture dish, dry 3d under 25 ℃ can obtain transparent Zn 2Al-TbEDTA LDHs film.
With Zn 2The XRD spectra and the Zn of Al-TbEDTA LDHs film 2The XRD spectra of Al-TbEDTA LDHs powder contrasts as can be known, Zn 2Only tangible LDHs (003), (006), (009) and (0012) characteristic diffraction peak occur in the XRD spectra of Al-TbEDTA LDHs film, and the characteristic diffraction peak of its (012), (015) and (110) (h, k ≠ 0) disappears, and shows Zn at low angle 2The particle of Al-TbEDTALDHs film is orientated along the c direction of principal axis.The SEM photo shows Zn 2The Al-TbEDTALDHs film surface is smooth, and most particles are the tiling attitude, and the section place can be observed tangible laminate structure, and thickness is 50 μ m.

Claims (2)

1. the preparation method of a highly oriented transparent dihydroxy metal oxide film, it is characterized in that: processing step is:
A. the preparation of hydrotalcite nano particle: directly adopt nucleation/crystallization isolation method, the inorganic anion intercalated houghite for preparing the nano-scale sheet structure by full back-mixing rotation liquid film reactor, wherein the concentration of mixed metal salt is 0.4～2.1M, laminate divalence, trivalent metal cation mol ratio M 2+/ M 3+Be 2～4: 1; Adopt ion exchange method, organic anion or title complex negatively charged ion are carried out ion-exchange with above-mentioned inorganic anion intercalated houghite, the generation interlayer is the anion intercalated hydrotalcite nano particle of organic anion or title complex; Having prepared interlayer respectively by above step is the anionic LDHs nanoparticle of inorganic anion, organic anion or title complex;
B. the preparation of highly oriented transparent hydrotalcite film: adopt solvent evaporated method to prepare the highly oriented transparent hydrotalcite film, the inorganic anion intercalated houghite of nano-scale sheet structure or organic anion or the anion intercalated hydrotalcite nano particle of title complex are dispersed in CO 2Water in, the preparation obtain the suspension that concentration is 0.1～0.4g/mL, at 20～80 ℃ of following direct evaporation solvents, obtain the highly oriented transparent hydrotalcite film;
Described laminate divalent metal M 2+Be Mg 2+, Ni 2+, Zn 2+, Fe 2+Or Cu 2+In a kind of, trivalent metal cation M 3+Be Al 3+, Fe 3+, Co 3+, Ti 3+Or Ga 3+In a kind of; Described inorganic anion is Cl -, NO 3 -, CO 3 2-Or SO 4 2-In a kind of; Described organic anion is a kind of in hexanodioic acid root, malonate, terephthaldehyde's acid group or the salicylate; Described title complex negatively charged ion is Tb (EDTA) -Or Fe (CN) 6 3-In a kind of; Wherein, EDTA is the ethylenediamine tetraacetic acid (EDTA) root.
2. preparation method according to claim 1 is characterized in that: described laminate divalent metal M 2+Be Mg 2+, Ni 2+Or Zn 2+In a kind of; Trivalent metal cation M 3+Be Al 3+Or Fe 3+In a kind of.
CNB2005101307817A 2005-12-29 2005-12-29 Preparation method of highly oriented transparent dihydroxy metal oxide film Expired - Fee Related CN100427401C (en)

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PCT/CN2006/001016 WO2007073639A1 (en) 2005-12-29 2006-05-18 Preparation method for highly orientated transparent thin film of double-layered-hydroxides

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CN101255556B (en) * 2008-03-28 2010-06-16 北京化工大学 Method for preparing porous zinc oxide particle studded composite film
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