CN1800028A - Preparation method of highly oriented transparent dihydroxy metal oxide film - Google Patents

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

Info

Publication number
CN1800028A
CN1800028A CN 200510130781 CN200510130781A CN1800028A CN 1800028 A CN1800028 A CN 1800028A CN 200510130781 CN200510130781 CN 200510130781 CN 200510130781 A CN200510130781 A CN 200510130781A CN 1800028 A CN1800028 A CN 1800028A
Authority
CN
China
Prior art keywords
ldhs
film
preparation
anion
hydrotalcite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 200510130781
Other languages
Chinese (zh)
Other versions
CN100427401C (en
Inventor
王连英
刘淼
段雪
李仓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CNB2005101307817A priority Critical patent/CN100427401C/en
Priority to PCT/CN2006/001016 priority patent/WO2007073639A1/en
Publication of CN1800028A publication Critical patent/CN1800028A/en
Application granted granted Critical
Publication of CN100427401C publication Critical patent/CN100427401C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • 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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a making method of high-oriented transparent bihydroxy composite metal oxide film, which comprises the following steps: adapting core-crystal separation method to prepare sheet-like LDHs nanometer particle with even grain size distribution; forming continual, high-oriented transparent LDHs film b directly by solvent evaporation method; preparing multifunctional LDHs film through controlling the kind and composition of host laminate metal element and interlaminar objective anion. The invention overcomes the limitation of LDHs powder material in the real appliance, which can be used in the photoelectric catalysis, separation and sensor.

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 Ni (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 lmin, 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, regulated pH=7 with NaOH solution, at 70 ℃, N 2Protection is carried out ion-exchange 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-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 120mL Na[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-TbEDTA LDHs film is orientated along the c direction of principal axis.The SEM photo shows Zn 2Al-TbEDTA 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 50 μ m.

Claims (4)

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; Or the employing ion exchange method, organic anion or title complex negatively charged ion and above-mentioned inorganic anion intercalated houghite are carried out ion-exchange, generating interlayer is the anion intercalated hydrotalcite nano particle of 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 hydrotalcite nano particle 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, obtain the highly oriented transparent hydrotalcite film.
2. preparation method according to claim 1 is characterized in that: hydrotalcite film main body 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.
3. preparation method according to claim 1 is characterized in that: hydrotalcite film 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.
4. preparation method according to claim 1 is characterized in that: the hydrotalcite film interlayer anion is inorganic anion, organic anion or title complex negatively charged ion; 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) -(EDTA=ethylenediamine tetraacetic acid (EDTA) root), Zn (BPS) 3 4-(BPS=4,7-phenylbenzene-1,10-phenanthroline disulfonic acid root) or Fe (CN) 6 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)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CNB2005101307817A CN100427401C (en) 2005-12-29 2005-12-29 Preparation method of highly oriented transparent dihydroxy metal oxide film
PCT/CN2006/001016 WO2007073639A1 (en) 2005-12-29 2006-05-18 Preparation method for highly orientated transparent thin film of double-layered-hydroxides

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005101307817A CN100427401C (en) 2005-12-29 2005-12-29 Preparation method of highly oriented transparent dihydroxy metal oxide film

Publications (2)

Publication Number Publication Date
CN1800028A true CN1800028A (en) 2006-07-12
CN100427401C CN100427401C (en) 2008-10-22

Family

ID=36810290

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005101307817A Expired - Fee Related CN100427401C (en) 2005-12-29 2005-12-29 Preparation method of highly oriented transparent dihydroxy metal oxide film

Country Status (2)

Country Link
CN (1) CN100427401C (en)
WO (1) WO2007073639A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100430132C (en) * 2006-09-27 2008-11-05 北京化工大学 Preparation of catalyst for synthesizing hydrotalcite thin film by alcohol oxidation reaction
WO2009036660A1 (en) * 2007-09-21 2009-03-26 Beijing University Of Chemical Technology A method for preparing film of layered double hydroxides
CN1994888B (en) * 2007-01-12 2010-05-19 北京化工大学 Cleaning preparation method of sheet-like composite oxide powder
CN101255556B (en) * 2008-03-28 2010-06-16 北京化工大学 Method for preparing porous zinc oxide particle studded composite film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113998716A (en) * 2021-12-09 2022-02-01 东莞理工学院 Method for regulating and controlling open-circuit voltage of water evaporation power generation device

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266356A (en) * 1991-06-21 1993-11-30 The Center For Innovative Technology Method for increasing the corrosion resistance of aluminum and aluminum alloys
US5474715A (en) * 1992-09-10 1995-12-12 Tdk Corporation Photochromic material, photochromic thin film, clay thin film, and their preparation
EP1069074B1 (en) * 1999-07-14 2003-01-08 RYOWA Corporation Film-forming composition and process for its production
CN1288078A (en) * 1999-09-14 2001-03-21 北京化工大学 Method for synthesis of well-dispersed and super fine anion laminated material
CN1142117C (en) * 2000-12-14 2004-03-17 北京化工大学 All return mixing-liquid film reactor and use in prepairng ultrafine anion layer shape material
US6979708B2 (en) * 2001-08-23 2005-12-27 Sunoco, Inc. (R&M) Hydrotalcites, syntheses, and uses
CN1507944A (en) * 2002-12-18 2004-06-30 北京化工大学 Method for clean synthesizing magnesite-alumina hydrotalcite
CN1222467C (en) * 2003-10-23 2005-10-12 浙江大学 Method of preparing bimetal oxide and hydrotalcite
CN1318454C (en) * 2003-11-13 2007-05-30 北京化工大学 Preparing nano sheet type polymer using LDHs as template and its preparing method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100430132C (en) * 2006-09-27 2008-11-05 北京化工大学 Preparation of catalyst for synthesizing hydrotalcite thin film by alcohol oxidation reaction
CN1994888B (en) * 2007-01-12 2010-05-19 北京化工大学 Cleaning preparation method of sheet-like composite oxide powder
WO2009036660A1 (en) * 2007-09-21 2009-03-26 Beijing University Of Chemical Technology A method for preparing film of layered double hydroxides
CN101255556B (en) * 2008-03-28 2010-06-16 北京化工大学 Method for preparing porous zinc oxide particle studded composite film

Also Published As

Publication number Publication date
CN100427401C (en) 2008-10-22
WO2007073639A1 (en) 2007-07-05

Similar Documents

Publication Publication Date Title
Safarpour et al. A review on two-dimensional metal oxide and metal hydroxide nanosheets for modification of polymeric membranes
CN101245151B (en) Hydrotalcite/polyalcohol composite self-supporting thin film and manufacture method thereof
Liu et al. Regulating the interlayer spacing of graphene oxide membranes and enhancing their stability by use of PACl
CN100560502C (en) Laminated double-metal hydroxide film that a kind of even compact is transparent and preparation method thereof
Siddiqui et al. Hydrothermally synthesized micron sized, broom-shaped MoSe2 nanostructures for superior photocatalytic water purification
Seisenbaeva et al. Solution equilibrium behind the room-temperature synthesis of nanocrystalline titanium dioxide
CN100427401C (en) Preparation method of highly oriented transparent dihydroxy metal oxide film
CN111777068A (en) Novel chloride ion removing material Ti3C2TxPreparation method and application of/Ag
Yan et al. The biomimetic synthesis of zinc phosphate nanoparticles
Chen et al. Comparison of the evolution and growth processes of films of M/Al-layered double hydroxides with M= Ni or Zn
Sun et al. Solvothermal synthesis of BiOCl flower-like hierarchical structures with high photocatalytic activity
Zou et al. Morphology-tunable synthesis and characterizations of Mg (OH) 2 films via a cathodic electrochemical process
Oaki Morphology design of crystalline and polymer materials from nanoscopic to macroscopic scales
Hur et al. New approach to the synthesis of layered double hydroxides and associated ultrathin nanosheets in de-ionized water by laser ablation
Koilraj et al. Adsorption characteristics of arsenate on colloidal nanosheets of layered double hydroxide
Bi et al. Self-assembly of immobilized titanate films with different layers for heavy metal ions removal from wastewater: Synthesis, modeling and mechanism
Xaba et al. SYNTHESIS OF SILVER SULFIDE NANOPARTICLES THROUGH HOMOGENEOUS PRECIPITATION ROUTE AND THE PREPARATION OF THE Ag 2 S-CHITOSAN NANOCOMPOSITES FOR THE REMOVAL OF IRON (II) ION FROM WASTEWATER.
Zhao et al. Orientated anatase TiO 2 nanocrystal array thin films for self-cleaning coating
Hong et al. Synthesis of flower-like silver nanoarchitectures at room temperature
CN102976373A (en) Method for synthesizing monodisperse stable LDHs (layered double hydroxides) colloid nanocrystalline
CN1776030A (en) Highly oriented laminated dihydroxy composite metal oxide film and its preparing method
Liu et al. Self-Construction of Core–Shell TiO2: A Colloidal-Molecular Mediated Recrystallization Process
CN106111104A (en) Lamellar zinc silicon layer dihydroxy complex hydroxide photocatalyst preparation method and application
WO2023066943A1 (en) Clay janus nanosheets
CN108002414A (en) A kind of method that hydrotalcite is prepared using coal dust as template

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20081022

Termination date: 20100129