Preparation of Layered Perovskite-Organic Composites and their Application to Photo-induced Electroconduction

层状钙钛矿有机复合材料的制备及其在光诱导导电中的应用

• 批准号: 10555221
• 负责人: SUGAHARA Yoshiyuki
• 金额: $ 6.85万
• 依托单位: Waseda University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10555221/
• 关键词: Layered perovskite; Aurivillius phases; Acid treatment; Protonated compounds; Intercalation; Photochromism; Redox reaction; Electronic conductivity; 無機-有機複合体; 有機修飾; アルコール; カルボン酸; 低酸化Nb; 光化学的性質; 無機・有機複合体; アルキルアミン

Preparation of new protonated layered perivskiteSince the number of layered perovskits is very limited, we found a novel route to prtonated layered perovskites. Aurivillius phases (Bi_2O_2[A_<n-1>B_nO_<3n+1>] ; n=3, A=(Sr, Na), B=Nb ; n=2, A=Sr, B=Ta ; n=2, without A-ions, B=W) were acid-treated at room temperature. Bismuth oxide sheets were selectively leached, and the structures of perovskite-like slabs were retained. For charge compensation, protons were introduced to form protonated layered perovskites with new compositions.Preparation of inorganic-organic hybridsLayered perovskite H[LaNb_2O_7] with interlayer surface modifled with alkoxyl groups was prepared. Using n-alkoxyl derivatives as intermediates, H[LaNb_2O_7] can be modified with various alcohols. In a similar fashion, H[LaNb_2O_7] can be modified with silanol-terminated poly(dimetylsiloxane) (HO(SiMe_2O)_mH).Preparation of intercalation compoundsH_<1.8>[Bi_<0.2>Sr_<0.8>Nb_2O_7] prepared via selective leaching from an Aurivillius phase Bi_2SrTa_2O_9 was allowed to react with n-alkylamines. All the n-alkylamines can form intercalation compounds via an acid-base reaction.Ptotochromism upon UV irradiationA methoxyl derivative of H[LaNb_2O_7] turned brue when it was irradiated with UV light. The blue color vanished gradually in air, but it can develop again upon UV irradiation. The electrical resistivity of the colored sample was significantly larger than that of the uncolored sample.

新型质子化层状钙钛矿的制备由于层状钙钛矿的数量非常有限，我们找到了一种制备质子化层状钙钛矿的新途径。 Aurivilius 相 (Bi_2O_2[A_<n-1>B_nO_<3n+1>] ; n=3, A=(Sr, Na), B=Nb ; n=2, A=Sr, B=Ta ; n=2, 无 A-离子, B=W) 在室温下进行酸处理。氧化铋片被选择性浸出，并保留了类钙钛矿板的结构。为了进行电荷补偿，引入质子形成具有新成分的质子化层状钙钛矿。无机-有机杂化材料的制备制备了层间表面烷氧基修饰的层状钙钛矿H[LaNb_2O_7]。以正烷氧基衍生物为中间体，H[LaNb_2O_7]可以用各种醇进行改性。以类似的方式，H[LaNb_2O_7]可以用硅烷醇封端的聚（二甲基硅氧烷）（HO（SiMe_2O）_mH）进行改性。通过从Aurivilius相Bi_2SrTa_2O_9中选择性浸出制备插层化合物H_<1.8>[Bi_<0.2>Sr_<0.8>Nb_2O_7] 可以与正烷基胺反应。所有的正烷基胺都可以通过酸碱反应形成插层化合物。紫外光照射下的光致变色现象H[LaNb_2O_7]的甲氧基衍生物在紫外光照射下变成蓝色。蓝色在空气中逐渐消失，但在紫外线照射下又会重新显现。有色样品的电阻率明显大于未着色样品的电阻率。

项目成果

Y.Sugahara et al.: "Preparation of a Protonated Form of a Layered Perovskite by Selective Leaching of Bismuth Oxide Sheets"Proe.18th International Japan-Korea Seminar on Ceramics. 203-207 (2001)

Y.Sugahara等人：“通过选择性浸出氧化铋片制备层状钙钛矿的质子化形式”Proe.18th国际日韩陶瓷研讨会。

Sugimoto, W., Shirata, M., Sugahara, Y. & Kuroda, K.: "New Conversion Reaction of an Aurivillius Phase into the Protonated Form of the Layered Perovskite by the Selective Leaching of the Bismuth Oxide Sheet"J. Am. Chem. Soc.. 121. 11602-3 (1999)

杉本 W.、白田 M.、菅原 Y.

W.Sugimoto et al.: "Structure and Semiconducting Properties of Carrier-Doped Niobates with a Four-Layered Perovskite Structure"J.Solid State Chem.. 148. 508-551 (1999)

W.Sugimoto 等人：“具有四层钙钛矿结构的载流子掺杂铌酸盐的结构和半导体性能”J.Solid State Chem.. 148. 508-551 (1999)

Tsunoda, Y., Shirata, M., Sugimoto, W., Y., Liu, Z., Terasaki, O., Kuroda, K. & Sugahara, Y.: "Preparation and HREM Characterization of a Protonated Form of a Layered Perovskite Tantalate from an Aurivillius Phase Bi_2SrTa_2O_9 via Acid Treatment"Inorg. C

角田，Y.，白田，M.，杉本，W.，Y.，刘，Z.，寺崎，O.，黑田，K.

Shirata, M., Tsunoda, Y., Sugimoto, W. & Sugahara, Y.: "Conversion of an Aurivillius Phase Bi_2SrNaNb_3O_<12> into Its Protonated Form via Treatment with Various Mineral Acids"Mater. Res. Soc. Symp. Proc.. 658. GG6.24.1-5 (2001)

白田，M.，角田，Y.，杉本，W.