Synthesis of Organic-Inorganic Nano-Composite Materials by the Assistance of Molecular Assembly Films and Investigation on Their Photo-and Electro-Chemical Properties

分子组装膜辅助有机-无机纳米复合材料的合成及其光电化学性能研究

• 批准号: 06453117
• 负责人: KAGAWA Shuichi
• 金额: $ 4.67万
• 依托单位: Nagasaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06453117/
• 关键词: Molecular film; Organic-inorganic nano-composite film; Nano level; Metal sulfide; Bimetallic sulfide; Metal selenide; Gold particulate; Third-order optical nonlinearity; Langmuir-Blodgett膜; 二分子膜; 量子サイズ; 有機-無機ナノ複合薄膜; 無機ナノ物質; 縮退4波混合; 無機-有機ナノ複合

Exposure of metal ion-containing organized molecular assembly (OMA) films to H_2S gas resulted in the formation of size-quantized metal sulfides such as ZnS,CdS,PbS and Cu_2S in OMA films. When the metal sulfide-bearing composite films were subjected repeatedly to a set of immersion in aqueous solutions of the corresponding metal ions (I) and the exposure to H_2S gas (S), the growth of metal sulfides within a nano-order level was observed. The size of CdS formed in OMA films could be also controlled precisely by the occupied molecular area of OMA-constructing amphiphiles and the repetition number of the I-S cycle. Futhermore, synthesis of bimetallic sulfides in OMA films was also investigated. Mixed metal sulfides (M_zN_<1-z>S) were obtained by the sulfidation of salt-form Langmuir-Blodgett films containing both M and N ions, while Core (MS)-shell (NS) type binary metal sulfides ([MS]_x[NS]_y)were obtained by conbining I-S cycles for MS formation and those for NS formation in series. It was also found that the repeated cycle of intercalation of precursor ions and transformation of the precursor into inorganic compounds was applicable to synthesis of various organic-inorganic nano-composite systems, such as metal selenide- and Au particulate-bearing composite systems.Nonlinear optical properties of the metal sulfide-bearing composite system was evaluated by third harmonic generation and degenerate four-wave mixing techniques. The third-order optical nonlinearity of PbS-bearing composite system was comparable to or even larger than hitherto reported systems and was optimized by the regulation of the amount and size of PbS.

含金属离子的有序分子组装（OMA）薄膜暴露于H2S气体中，导致在OMA薄膜中形成尺寸量子化的金属硫化物，如ZnS、CdS、PbS和Cu 2S。将含金属硫化物的复合膜反复浸泡在相应金属离子的水溶液中（I）和暴露在H_2S气体中（S），观察到纳米级金属硫化物的生长。OMA膜中CdS的尺寸也可以通过OMA两亲分子的占据面积和I-S循环的重复次数来精确控制。此外，还研究了OMA薄膜中硫化物的合成。混合金属硫化物（M_zN_<1-z>S）是由含M和N离子的盐型LB膜硫化得到的，而核（MS）-壳（NS）型二元金属硫化物（[MS]_x[NS]_y）是由形成MS和形成NS的I-S循环串联得到的。研究发现，前驱体离子的插入和前驱体转化为无机化合物的重复循环适用于各种有机-无机纳米复合体系的合成，如含金属硒化物和含Au微粒的复合体系。含PbS复合体系的三阶光学非线性系数与已有报道的体系相当甚至更大，并通过调节PbS的含量和尺寸得到优化。

项目成果

T.Fukumi: "Degenerate Four-Wave Mixing Study of Nonlinear Optical Property of PbS Micro-Crystallites Embedded in Langmuir-Blodgett Films" Nonlinear Optics. 13. 153-156 (1995)

T.Fukumi：“嵌入 Langmuir-Blodgett 薄膜中的 PbS 微晶非线性光学特性的简并四波混合研究”非线性光学。

I.Moriguchi: "Novel Multilayr Film Incorporating Electro-and Photo-Chemically Active Decatungstate Anion" Chemistry Letters. 1994. 691-694 (1994)

I.Moriguchi：“结合电和光化学活性十钨酸阴离子的新型多层薄膜”化学快报。

I.Moriguchi: "Stepwise Growth of Size-confined CdS in the Two-Dimensional Hydrophilic Interlayers of Langmuir-Blodgett Fims by the Repeated Sulfidation-Intercalation Technique" Journal of The Chemical Society,Faraday Transaction. 90. 349-354 (1994)

I.Moriguchi：“通过重复硫化插层技术在 Langmuir-Blodgett 薄膜的二维亲水夹层中逐步生长尺寸限制的 CdS”，化学会杂志，法拉第汇刊。

森口 勇: "分子膜金-金属ポリ酸イオン複合体の調製と特性" 高分子加工. 45. 8-13 (1996)

Isamu Moriguchi：“分子膜金-金属多元酸离子配合物的制备和性能”聚合物加工45. 8-13 (1996)。

Isamu Moriguchi: "Control of Size of CdS Formed in Organized Molecular Assembly Films by Molecular Structure and Film Orderliness" Chemistry Letters. 1995. 761-762 (1995)

Isamu Moriguchi：“通过分子结构和薄膜有序性控制有序分子组装薄膜中形成的 CdS 尺寸”化学快报。