WO2009036660A1 - Procédé de préparation de film d'hydroxydes doubles lamellaires - Google Patents

Procédé de préparation de film d'hydroxydes doubles lamellaires Download PDF

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WO2009036660A1
WO2009036660A1 PCT/CN2008/070857 CN2008070857W WO2009036660A1 WO 2009036660 A1 WO2009036660 A1 WO 2009036660A1 CN 2008070857 W CN2008070857 W CN 2008070857W WO 2009036660 A1 WO2009036660 A1 WO 2009036660A1
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film
solution
ldhs
open container
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Lianying Wang
Yingchao Zhang
Yipeng Wang
Ping Yin
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/006—Compounds containing zinc, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention is in the field of layered double hydroxides, and in particular provides a method for preparing a layered bimetallic hydroxide film. Background technique
  • LDHs Layered double hydroxides, also known as hydrotalcites (LDHs), are an important inorganic functional material. LDHs have a layered structure, and the composition of the main lamellar elements, the types and amounts of guest anions in the interlayers are all controllable. These characteristics make LDHs have a variety of excellent physicochemical properties, and have a very broad application prospect in many fields such as ion exchange, adsorption, catalysis, polymer modification, optical materials, magnetic materials, and electrical materials. At present, the research and application of LDHs at home and abroad are generally limited to LDHs powder materials. However, LDHs powder materials have the disadvantages of easy loss and difficulty in recovery. Compared with the powder material, the membrane material is more favorable for deviceization, which will greatly expand the industrial application of LDHs, and the functional properties of the optical, optical, magnetic and other aspects of the oriented film will be greatly improved. .
  • LDHs are not easily prepared into thin films, thus hindering some application development and deviceization of LDHs materials.
  • methods for preparing LDHs films reported in the literature, mainly in one-step synthesis and two-step synthesis. Examples of one-step synthesis are: Document Oie. L£ ⁇ ., 2005, 34, 1610, Lei et al. first sulfonated the polystyrene substrate with concentrated sulfuric acid, and then prepared the surface by using the urea method. Oriented dense Mg-Al hydrotalcite film; in the literature Ai v. Mater., 2006, 18, 3089, Duan et al.
  • M-A1 hydrotalcite film used anodized aluminum/aluminum as the substrate to prepare superhydrophobic properties by in-situ growth method.
  • M-A1 hydrotalcite film examples of two-step synthesis are: In the literature Ai v. Mater., 2001, 13, 1263, Gandner et al. first prepared a colloid of LDHs, which was then cast on a glass substrate to obtain a magnesium oxide intercalated layer. Aluminum LDHs film; in the literature Thin Solid Films, 2001, 397, 255, Akihiko et al. used LB method to first load a negatively charged base metal complex on a mica substrate, and then use it with positively charged LDHs particles.
  • a hybrid film of Ni-Al hydrotalcite and a ruthenium-containing metal complex was prepared by electrostatic action; in the literature C eo., 2007, 2, 123, Wang et al. first prepared uniformly dispersed LDHs nanoparticles, and then adopted " Solvent evaporation method LDHs film. Summary of the invention
  • the object of the present invention is to provide a method for preparing a uniformly dense and transparent layered double hydroxide film, which can be uniformly prepared at the air-water interface under the action of surface tension and pH gradient of the solution without substrate support. Dense and transparent LDHs film for deviceization of multifunctional materials LDHs.
  • the uniform dense and transparent layered double hydroxide film provided by the invention is formed at the interface of air and water, and the support of the substrate is not required in the film formation process, thereby overcoming the influence of the substrate on the preparation of the LDHs film.
  • the method for preparing a layered double hydroxide film of the present invention comprises placing an open container containing a mixed salt solution and an open container containing an aqueous ammonia solution in the same closed environment, wherein:
  • the mixed salt solution contains a soluble divalent metal salt and a soluble trivalent metal salt, and the total molar concentration of the divalent metal ion and the trivalent metal ion is 0.1-0.3 mol/L, and the molar concentration of the divalent metal ion and the trivalent metal ion
  • the ratio is 2-4: 1; the divalent metal ion is selected from one or more of Mg 2+ , Ni 2+ , Co 2+ , Zn 2+ , Fe 2+ and Cu 2+ ; One or more of Al 3+ , Cr 3+ , Fe 3+ , Ga 3+ , In 3+ ; the anion in solution is selected from N0 3 —, Cl—, F—, Br—, and S0 4 2 - one or several of them.
  • the aqueous ammonia solution in the open container volatilizes ammonia, and the volatilized ammonia reacts with the divalent metal salt and the trivalent metal salt in the liquid surface of the mixed salt solution, and the surface tension of the solution
  • a uniform and transparent LDHs film was prepared at the air-water interface in combination with a pH gradient.
  • the divalent metal ion is preferably Ni 2+ and/or Zn 2+
  • the trivalent metal ion is preferably Al 3+ and/or Fe 3+
  • the anion is preferably N0 3 —, C1 — and S0 4 One or more of 2 - more preferably N0 3 -.
  • the open container containing the mixed salt solution is preferably placed above the open container containing the aqueous ammonia solution during the placement.
  • the volume ratio of the mixed salt solution to the aqueous ammonia solution may be 0.5-2.
  • FIG. 1 is a schematic diagram of a gas-liquid interface reaction, Wherein, 1 denotes a dryer; 2 denotes an open container containing a mixed salt solution; 3 denotes an open container containing an aqueous ammonia solution; and 4 denotes a layered double metal hydroxide film.
  • the open container can be any conventional open container that can be used for chemical reactions, for example, a beaker, a culture dish, preferably a culture dish.
  • the conditions for the placement include a temperature of 10 to 45 ° C, preferably 20 to 30 ° C; and a time of 2 to 48 hours, preferably 4 to 24 hours.
  • the pressure in the closed environment may be negative pressure, normal pressure or positive pressure, preferably atmospheric pressure.
  • the concentration of the aqueous ammonia solution is preferably from 0.5 to 2% by weight under normal pressure. When the pressure in the closed environment is negative, the concentration of the aqueous ammonia solution can be appropriately lowered; when the pressure in the closed environment is positive, the concentration of the aqueous ammonia solution can be appropriately increased.
  • the film product may also be recovered after the open container containing the mixed salt solution and the open container containing the aqueous ammonia solution, and the method of recovering the film product may include using the film at the air-water interface.
  • the water was washed with 0 2 to remove unreacted salt, and then the film was transferred to a substrate and dried at 10 to 40 °C.
  • the substrate may be a slide, a silicon wafer or a silicon dioxide sheet.
  • the above materials were characterized by XRD, IR, TG-DTA, elemental analysis and FESEM. It was proved that the uniform and transparent LDHs films were successfully prepared by this method.
  • the IR of the ground powder proves that the interlayer anion is nitrate, and the 001 series diffraction peak unique to the LDHs material also appears in the XRD spectrum, which indicates that Typical nitrate-type LDHs; SEM images of the film show that the surface of the LDHs film is smooth and compact, and the particle size is nanometer-scale and highly ordered and evenly distributed.
  • the invention has the advantages of: room temperature reaction, low energy consumption; gas-liquid interface film formation, no substrate support during film formation, overcomes the influence of the substrate on the preparation of LDHs film; the film surface is smooth and flat, both macroscopically and microscopically Highly ordered nanostructures; The type and composition of LDHs laminate metal elements and interlayer anions can be adjusted as needed to obtain multifunctional LDHs films; one-step reaction, simple equipment and easy operation.
  • Figure 1 is a schematic diagram of the gas-liquid interface reaction.
  • 2 is an XRD spectrum of the powder after grinding of the M 2 AlN0 3 LDHs film obtained in Example 1, the abscissa is 2 ⁇ , unit: degree; and the ordinate is intensity.
  • 3 is a FT-IR spectrum of the powder after grinding of the Ni 2 AlN0 3 LDHs film obtained in Example 1, the abscissa is the wave number, the unit is cm- 1 ; the ordinate is the transmittance.
  • Example 4 is a field emission electron scanning electron microscope (FESEM) photograph of the Ni 2 AlN0 3 LDHs film obtained in Example 1 at a magnification of 10,000 times.
  • FESEM field emission electron scanning electron microscope
  • Example 5 is a field emission electron scanning electron microscope (FESEM) photograph of a Ni 2 AlN0 3 LDHs film obtained in Example 1 at a magnification of 100,000 times.
  • the FT-IR spectrum was obtained on VECTOR 22 (Brook, Germany), and the sample was mixed with KBr and compressed, and scanned at room temperature under an air atmosphere.
  • the parameter indicators are: resolution of 4 cm - 1 and scanning range of 4000-400 cm.
  • Example 1 The surface morphology of the film was observed by a Japanese Hitachi S-4700 field emission scanning electron microscope. The sample was sprayed with gold on the surface before the test to avoid discharge of the sample during the test. The acceleration voltage during the test was 20 kV.
  • Example 1 The surface morphology of the film was observed by a Japanese Hitachi S-4700 field emission scanning electron microscope. The sample was sprayed with gold on the surface before the test to avoid discharge of the sample during the test. The acceleration voltage during the test was 20 kV.
  • Step A 1.1604 g (0.004 mol) of solid ⁇ ( ⁇ 0 3 ) 2 ⁇ 6 ⁇ 2 0 and 0.7503 g (0.002 mol) of solid ⁇ 1( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 were dissolved in 20 ml of de-C0 2 water. A mixed salt solution was obtained.
  • Step B amount of 0.54ml mass percent concentration of 28% concentrated aqueous ammonia, rinsed with C0 2 was diluted with water to 20ml to give a mass concentration of 0.68% dilute aqueous ammonia.
  • Step C Place the mixed salt solution and ammonia water in different culture dishes, place the culture dish in a sealed desiccator (produced by Beijing Longyuan Glass Factory, diameter 160mm), and place at normal pressure 25 °C. hour. Then, a part of the film on the surface of the mixed salt solution was taken out and washed with de-O 2 water to a residue-free salt, and then the film was transferred to a clean silicon substrate and dried at 20 ° C to obtain a film sample. After rinsed with the remaining portion of the film was removed by centrifugation C0 2 water washed free of residual salts, and dried 60 ° C for 24 hours and ground to give a powder Ni 2 AlN0 3 LDHs.
  • a sealed desiccator produced by Beijing Longyuan Glass Factory, diameter 160mm
  • the IR spectrum of Ni 2 AlN0 3 LDHs powder is strong and sharp at 1384 cm- 1 .
  • the sharp characteristic absorption peak is the v 3 of the nitrate antisymmetric stretching vibration peak, and as shown in Fig. 2, in the XRD spectrum, a series of diffraction peaks unique to LDHs appear in the vicinity of 10°, 20 ° and 61°, and the product The particle size is 4.75 nm.
  • the FESEM photograph of the film sample showed that the film surface was smooth and compact, and the particle size results were basically consistent with those calculated by XRD.
  • Step A 4.3360 g (0.016 mol) of solid ⁇ ( ⁇ 0 3 ) 2 ⁇ 6 ⁇ 2 0 and 3.0012 g (0.008 mol) of solid ⁇ 1( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 were dissolved in 80 ml of de-C0 2 water. A mixed salt solution was obtained.
  • Step B amount of 2.16ml mass percent concentration of 28% concentrated aqueous ammonia, rinsed with C0 2 was diluted with water to 80ml to give a mass concentration of 0.68% dilute aqueous ammonia.
  • Step C The mixed salt solution and the dilute ammonia water were placed in separate petri dishes, and the petri dishes were placed in a sealed desiccator and allowed to stand at a normal pressure of 20 ° C for 12 hours. Then, a part of the film on the surface of the mixed salt solution was taken out and washed with 0 2 water until no residual salt, and then the film was transferred to a clean glass slide and dried at 40 ° C to obtain a film sample. After rinsed with the remaining portion of the film was removed by centrifugation C0 2 water washed free of residual salts, and dried 60 ° C for 24 hours and ground to give a powder Zn 2 AlN0 3 LDHs.
  • Step A 1.1604 g (0.004 mol) of solid ⁇ ( ⁇ 0 3 ) 2 ⁇ 6 ⁇ 2 0 and 0.8080 g (0.002 mol) of solid Fe(N0 3 ) 3 *9H 2 0 were dissolved in 80 ml of de-C0 2 water. A mixed salt solution was obtained.
  • Step B amount of 1.25ml mass percent concentration of 28% concentrated aqueous ammonia, rinsed with C0 2 was diluted with water to 20ml to give a concentration of 1.57% by mass percentage of dilute aqueous ammonia.
  • Step C The mixed salt solution and the dilute ammonia water were placed in separate petri dishes, and the petri dishes were placed in a sealed desiccator and allowed to stand at normal pressure of 30 ° C for 8 hours. Then, part of the film on the surface of the mixed salt solution is taken out and washed with 0 2 water until there is no residual salt, and then transferred to a clean silicon substrate. Drying was carried out at 10 ° C to obtain a film sample. The remaining portion of the film was taken out and washed by centrifugation with co 2 water to a residue-free salt, dried at 60 ° C for 24 hours and ground to obtain a Ni 2 FeN 0 3 LDHs powder.
  • the strong and sharp characteristic absorption peak appearing at 1384 cm- 1 in the IR spectrum of Ni 2 FeN0 3 LDHs powder is the v 3 anti-symmetric stretching vibration peak of nitrate, and in the XRD spectrum, 2 ⁇ is 10°, 20 0 and A series of diffraction peaks unique to LDHs appeared near 61 °.
  • FESEM photographs of the film samples show that the film consists of nanoscale particles with a smooth, compact surface.

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Description

一种层状双金属氢氧化物薄膜的制备方法
技术领域
本发明属于层状双金属氢氧化物领域，特别提供了一种层状双金属氢氧 化物薄膜的制备方法。 背景技术
层状双金属氢氧化物也称类水滑石（LDHs ) , 是一种重要的无机功能材 料。 LDHs具有层状结构， 其主体层板元素组成、 层间客体阴离子种类和数 量等均有可调控性。 这些特点使 LDHs具有多种优异的物理化学特性， 在离 子交换、 吸附、 催化、 高分子改性、 光学材料、 磁学材料、 电学材料等许多 领域展现出极为广阔的应用前景。 目前， 国内外对 LDHs的研究和应用一般 均局限于 LDHs粉体材料， 然而 LDHs粉体材料存在着易流失、 回收困难等 缺点。 相对于粉体材料， 膜材料更有利于器件化， 这将大大拓宽 LDHs在工 业上的应用， 而且对于取向性的薄膜， 其电、 光、 磁等各方面的功能性都会 有很大的提高。
与其它层状材料不同的是， LDHs不易制备成薄膜， 因而阻碍了 LDHs 材料的一些应用开发以及器件化。 目前文献报道的关于 LDHs薄膜的制备方 法有限， 主要有一步合成法和两步合成法两大类。 一步合成法的实例有： 文 献 Oie . L£^. , 2005, 34， 1610中， Lei等首先将聚苯乙烯基片用浓硫酸进行 磺化处理，之后利用尿素法在其表面制备得到了垂直取向致密的 Mg-Al水滑 石薄膜； 文献 Ai v. Mater., 2006, 18, 3089中， Duan等人以阳极氧化铝 /铝为基 片， 采用原位生长法制备得到了具有超疏水性能的 M-A1水滑石薄膜。 两步 合成法的实例有： 文献 Ai v. Mater.， 2001， 13， 1263中， Gandner等人首先制 备得到 LDHs的胶体， 之后将其浇铸沉积在玻璃基片上获得了垸氧基插层的 镁铝 LDHs膜； 文献 Thin Solid Films, 2001 , 397, 255中， Akihiko等人利用 LB 的方法首先在云母基片上负载了带负电荷的钌金属配合物， 之后利用其 与带正电荷的 LDHs粒子间的静电作用制备了 Ni-Al水滑石与含钌金属配合 物的杂化薄膜； 文献 C e o 聽.， 2007， 2， 123中， Wang等人首先制备 得到均匀分散的 LDHs纳米粒子， 然后采用"溶剂蒸发法"将其有序组装制备 LDHs薄膜。 发明内容
本发明的目的在于提供一种均匀致密透明的层状双金属氢氧化物薄膜 的制备方法， 该方法无需基片支撑， 在溶液的表面张力和 pH梯度共同作用 下在空气一水界面处制备均匀致密透明的 LDHs 薄膜， 以实现多功能材料 LDHs的器件化。
本发明提供的均匀致密透明的层状双金属氢氧化物薄膜， 膜是在空气一 水的界面处形成的， 成膜过程中无需基片的支撑， 克服了基片对 LDHs薄膜 制备的影响。
本发明的层状双金属氢氧化物薄膜的制备方法包括将盛有混合盐溶液 的敞口容器和盛有氨水溶液的敞口容器在同一密闭环境中放置， 其中：
混合盐溶液含有可溶性二价金属盐和可溶性三价金属盐， 二价金属离子 和三价金属离子的总的摩尔浓度为 0.1-0.3mol/L， 二价金属离子和三价金属 离子的摩尔浓度比为 2-4: 1； 二价金属离子选自 Mg2+、 Ni2+、 Co2+、 Zn2+、 Fe2+和 Cu2+中的一种或几种； 三价金属离子选自 Al3+、 Cr3+、 Fe3+、 Ga3+、 In3+ 中的一种或几种； 溶液中的阴离子选自 N03—、 Cl—、 F―、 Br—和 S04 2—中的一 种或几种。
在本发明方法中， 在放置过程中， 盛于敞口容器的氨水溶液挥发出氨， 挥发的氨在混合盐溶液的液面与二价金属盐和三价金属盐反应，在溶液的表 面张力和 pH梯度共同作用下在空气-水界面处制备均匀致密透明的 LDHs薄 膜。
在混合盐溶液中，二价金属离子优选为 Ni2+和 /或 Zn2+，三价金属离子优 选为 Al3+和 /或 Fe3+; 阴离子优选为 N03—、 C1—和 S04 2—中的一种或几种， 更优 选为 N03—。
在放置过程中，盛有混合盐溶液的敞口容器优选位于盛有氨水溶液的敞 口容器的上方。
混合盐溶液和氨水溶液的体积比可以为 0.5-2。
所述密闭环境优选通过将盛有混合盐溶液的敞口容器和盛有氨水溶液 的敞口容器放置在密封的干燥器中而实现。 图 1为气液界面反应的示意图， 其中， 1表示干燥器； 2表示盛有混合盐溶液的敞口容器； 3表示盛有氨水溶 液的敞口容器； 4表示层状双金属氢氧化物薄膜。
所述敞口容器可以为常规的各种能够用于化学反应的敞口容器， 例如， 烧杯、 培养皿， 优选为培养皿。
放置的条件包括温度可以为 10-45°C，优选为 20-30°C ; 时间可以为 2-48 小时， 优选为 4-24小时。
密闭环境的压力可以为负压、 常压或正压， 优选为常压。 在常压下， 氨 水溶液的浓度优选为 0.5-2重量％。 当密闭环境的压力为负压时， 氨水溶液 的浓度可以适当降低； 当密闭环境的压力为正压时， 氨水溶液的浓度可以适 当增加。
在将盛有混合盐溶液的敞口容器和盛有氨水溶液的敞口容器放置之后， 还可以回收膜产品， 回收膜产品的方法可以包括将空气一水界面处的膜用去 。02水洗涤， 以除去未反应的盐， 然后将膜转移到基片上并在 10-40°C下进 行干燥。 所述的基片可以为载玻片、 硅片或二氧化硅片。
将上述材料进行 XRD、 IR、 TG-DTA、 元素分析、 FESEM表征证明利 用该方法成功制备得到了均匀致密透明的 LDHs薄膜。 例如， 实施例 1所获 得的 Ni2AlN03LDHs薄膜， 磨碎后的粉体的 IR证明层间阴离子为硝酸根， XRD谱图中也出现了 LDHs材料特有的 001系列衍射峰，这表明得到的是典 型的硝酸根型 LDHs; 膜的 SEM照片显示 LDHs薄膜表面光滑致密平整， 粒 径为纳米量级且高度有序， 均匀分布。
本发明优点在于： 室温反应， 能源消耗低； 气液界面成膜， 成膜过程中 无需基片的支撑， 克服了基片对 LDHs薄膜制备的影响； 膜表面光滑平整， 宏观和微观上都为高度有序的纳米结构； 可根据需要调控 LDHs层板金属元 素及层间阴离子的种类和组成， 得到多功能 LDHs薄膜； 一步反应， 设备简 单， 操作容易。 附图说明
图 1为气液界面反应的示意图。
图 2为实施例 1所获得的 M2AlN03LDHs薄膜磨碎后粉末的 XRD谱图， 横坐标为 2Θ, 单位： 度； 纵坐标为强度。 图 3为实施例 1所获得的 Ni2AlN03LDHs薄膜磨碎后粉末的 FT-IR谱图， 横坐标为波数， 单位： cm—1 ; 纵坐标为透过率。
图 4为实施例 1所获得的 Ni2AlN03LDHs薄膜放大 10， 000倍的场发射 电子扫描电子显微镜 （FESEM) 照片。
图 5为实施例 1所获得的 Ni2AlN03LDHs薄膜放大 100， 000倍的场发 射电子扫描电子显微镜 （FESEM) 照片。 具体实施方式
在以下实施例中， 使用如下方法测定各实施例中制得的产物：
以日本岛津 XRD-6000型 X射线衍射仪进行结构分析， Cu Ka光源（λ =
0.154 nm)， 电压 40 Kv， 电流 30 mA， 连续扫描， 扫描速度 5 min。
FT-IR光谱在 VECTOR 22 (德国布鲁克公司） 上获得， 样品与 KBr混 合后压片， 室温、 空气气氛下扫描。 参数指标为： 分辨率为 4 cm—1 , 扫描范 围 4000-400cm 。
利用日本 Hitachi S-4700 场发射扫描电子显微镜来观察膜表面的形貌， 样品在测试前表面喷金以避免测试时样品放电， 测试时的加速电压为 20kv。 实施例 1
步骤 A: 将 1.1604g (0.004mol) 的固体 Νΐ(Ν03)2·6Η20 和 0.7503 g (0.002mol) 的固体 Α1(Ν03)3·9Η20溶于 20ml的去 C02水中， 得到混合盐 溶液。
步骤 B: 量取 0.54ml质量百分比浓度为 28%的浓氨水， 用去 C02水稀 释到 20ml以得到质量百分比浓度为 0.68%的稀氨水。
步骤 C: 将混合盐溶液和氨水分别置于不同的培养皿中， 将培养皿放置 在密封的干燥器中 （北京龙源玻璃厂生产， 直径为 160mm)， 在常压 25°C下 放置 24小时。 然后将混合盐溶液表面的部分膜取出后用去 C02水洗涤至无 残余的盐， 之后将膜转移到干净的硅基片上 20°C下进行干燥， 得到膜样品。 剩余部分的膜取出后用去 C02水离心洗涤至无残余的盐， 60°C下干燥 24小 时并研磨， 得到 Ni2AlN03LDHs粉末。
如图 3所示， Ni2AlN03LDHs粉末的 IR谱图在 1384cm—1出现的强而尖 锐的特征吸收峰为硝酸根的 v3反对称伸缩振动峰， 而如图 2所示， 在 XRD 谱图中 2Θ为 10°、 20 °以及 61°附近出现了 LDHs特有的系列衍射峰， 产物 的粒径为 4.75nm。 如图 4和 5所示， 膜样品的 FESEM照片显示膜表面光滑 致密平整， 粒子粒径结果与由 XRD计算的基本一致。 实施例 2
步骤 A: 将 4.3360g (0.016mol) 的固体 Ζη(Ν03)2·6Η20 和 3.0012 g (0.008mol) 的固体 Α1(Ν03)3·9Η20溶于 80ml的去 C02水中， 得到混合盐 溶液。
步骤 B: 量取 2.16ml质量百分比浓度为 28%的浓氨水， 用去 C02水稀 释到 80ml以得到质量百分比浓度为 0.68%的稀氨水。
步骤 C: 将混合盐溶液和稀氨水分别置于不同的培养皿中， 将培养皿放 置在密封的干燥器中， 在常压 20°C下放置 12小时。 然后将混合盐溶液表面 的部分膜取出后用去 02水洗涤至无残余的盐，之后将膜转移到干净的载玻 片上 40°C下进行干燥， 得到膜样品。 剩余部分的膜取出后用去 C02水离心 洗涤至无残余的盐， 60°C下干燥 24小时并研磨， 得到 Zn2AlN03LDHs粉末。
Zn2AlN03LDHs粉末的 IR谱图中在 1384cm—1出现的强而尖锐的特征吸 收峰为硝酸根的 v3反对称伸缩振动峰， 而在 XRD谱图中 2Θ为 10°、 20 0以 及 61 °附近出现了 LDHs特有的系列衍射峰。 膜样品的 FESEM照片显示膜 由纳米级的粒子组成， 表面光滑致密平整。 实施例 3
步骤 A: 将 1.1604g (0.004mol) 的固体 Νΐ(Ν03)2·6Η20 和 0.8080 g (0.002mol) 的固体 Fe(N03)3*9H20溶于 80ml的去 C02水中， 得到混合盐 溶液。
步骤 B: 量取 1.25ml质量百分比浓度为 28%的浓氨水， 用去 C02水稀 释到 20ml以得到质量百分比浓度为 1.57%的稀氨水。
步骤 C: 将混合盐溶液和稀氨水分别置于不同的培养皿中， 将培养皿放 置在密封的干燥器中，在常压 30°C下放置 8小时。然后将混合盐溶液表面的 部分膜取出后用去 02水洗涤至无残余的盐， 之后转移到干净的硅基片上 10°C下进行干燥， 得到膜样品。剩余部分的膜取出后用去 co2水离心洗涤至 无残余的盐， 60°C下干燥 24小时并研磨， 得到 Ni2FeN03LDHs粉末。
Ni2FeN03LDHs粉末的 IR谱图中在 1384cm—1出现的强而尖锐的特征吸 收峰为硝酸根的 v3反对称伸缩振动峰， 而在 XRD谱图中 2Θ为 10°、 20 0以 及 61 °附近出现了 LDHs特有的系列衍射峰。 膜样品的 FESEM照片显示膜 由纳米级的粒子组成， 表面光滑致密平整。

Claims

权利要求书
1、 一种层状双金属氢氧化物薄膜的制备方法， 其特征在于， 该方法包 括将盛有混合盐溶液的敞口容器和盛有氨水溶液的敞口容器在同一密闭环 境中放置， 其中：
混合盐溶液含有可溶性二价金属盐和可溶性三价金属盐， 二价金属离 子和三价金属离子的总的摩尔浓度为 0.1-0.3mol/L， 二价金属离子和三价金 属离子的摩尔浓度比为 2-4: 1； 二价金属离子选自 Mg2+、 Ni2+、 Co2+、 Zn2+、 Fe2+和 Cu2+中的一种或几种； 三价金属离子选自 Al3+、 Cr3+、 Fe3+、 Ga3+、 In3+ 中的一种或几种； 溶液中的阴离子选自 N03—、 Cl—、 F―、 Br—和 S04 2—中的一 种或几种。
2、 根据权利要求 1所述的方法， 其中， 在混合盐溶液中， 二价金属离 子为 Ni2+和 /或 Zn2+， 三价金属离子为 Al3+和 /或 Fe3+; 阴离子为 N03_、 C1—和 S04 2_中的一种或几种。
3、 根据权利要求 1所述的方法， 其中， 盛有混合盐溶液的敞口容器位 于盛有氨水溶液的敞口容器的上方。
4、 根据权利要求 1或 3所述的方法， 其中， 混合盐溶液和氨水溶液的 体积比为 0.5-2。
5、 根据权利要求 1 所述的方法， 其中， 放置的条件包括温度为 10-45 V， 时间为 2-48小时， 压力为常压； 氨水溶液的浓度为 0.5-2重量％。
6、根据权利要求 5所述的方法，其中，放置的条件包括放置温度为 20-30 °C， 放置时间为 4-24小时。
7、 根据权利要求 1所述的方法， 其中， 在将盛有混合盐溶液的敞口容 器和盛有氨水溶液的敞口容器放置之后， 该方法还包括在盛有混合盐溶液的 敞口容器的液面上取出膜， 将膜用水洗涤， 然后转移到基片上并在 10-40°C 下进行干燥， 所述基片为载玻片、 硅片或二氧化硅片。
PCT/CN2008/070857 2007-09-21 2008-04-30 Procédé de préparation de film d'hydroxydes doubles lamellaires Ceased WO2009036660A1 (fr)

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