在没有聚集的层状钛酸盐薄膜透明的层间金纳米粒子的原位合成
Summary
在这里，我们提出了一个协议为原位合成层状钛酸盐薄膜的夹层空间内的黄金纳米粒子（纳米金）的无金纳米颗粒的聚集。即使4个月后没有观察到的光谱变化。合成的材料已预期在催化，光催化，并具有成本效益的电浆设备的开发应用程序。
Abstract
Combinations of metal oxide semiconductors and gold nanoparticles (AuNPs) have been investigated as new types of materials. The in situ synthesis of AuNPs within the interlayer space of semiconducting layered titania nanosheet (TNS) films was investigated here. Two types of intermediate films (i.e., TNS films containing methyl viologen (TNS/MV2+) and 2-ammoniumethanethiol (TNS/2-AET+)) were prepared. The two intermediate films were soaked in an aqueous tetrachloroauric(III) acid (HAuCl4) solution, whereby considerable amounts of Au(III) species were accommodated within the interlayer spaces of the TNS films. The two types of obtained films were then soaked in an aqueous sodium tetrahydroborate (NaBH4) solution, whereupon the color of the films immediately changed from colorless to purple, suggesting the formation of AuNPs within the TNS interlayer. When only TNS/MV2+ was used as the intermediate film, the color of the film gradually changed from metallic purple to dusty purple within 30 min, suggesting that aggregation of AuNPs had occurred. In contrast, this color change was suppressed by using the TNS/2-AET+ intermediate film, and the AuNPs were stabilized for over 4 months, as evidenced by the characteristic extinction (absorption and scattering) band from the AuNPs.
Introduction
各种贵金属纳米颗粒（的MNP）表现出特征的颜色或色调由于它们的局域型表面等离子体共振（LSPR）特性;因此，的MNP可以各种光学和/或光化学应用1-4中使用。最近，金属氧化物半导体（MOS）的光催化剂，如二氧化钛（TiO 2）和的MNP，组合已被彻底研究作为新型光催化剂5-14。然而，在许多情况下，存在该MOS表面上非常少量的MNP的，因为大多数的MOS颗粒具有相对低的表面积。另一方面，层状金属氧化物半导体（LMOSs）显示出光催化性能，还具有大的表面积，典型地几百平方米每一个LMOS 15-17的单位为g。此外，各种LMOSs具有插层性质（ 即，各种化学物质可被容纳他们的膨胀和大中间层的空间内）15-20。因此，具有的MNP和LMOSs的组合，预期相对大量的MNP都与半导体光催化剂杂交。
我们已经报道了铜纳米粒子（CuNPs）21改性活生物体的夹层空间内的原位合成第一，通过非常简单的步骤透明薄膜（二氧化钛纳米片TNS 16-30）。然而，尚未报道的合成方法的细节和其他贵金属的MNP和TNS杂种的表征。此外，TNS层内的CuNPs很容易被氧化和环境条件下，21脱色。因此，我们集中于金粒子（AuNPs），因为金纳米粒子被广泛用于各种光学，光化学，和催化的应用，并且预期他们将抗氧化3-5,7,8,10-14相对稳定，28,31,32。在这里，我们报告TNS和表演塔的夹层空间内金纳米粒子的合成ŧ2 ammoniumethanethiol（2-AET +; 图1插图）有效地工作，作为TNS的夹层内的金纳米粒子的保护剂。
Protocol
注意：化学品和解决方案时一定要小心。按照相应的安全实践和戴手套，眼镜和白大褂在任何时候。要知道，相比于他们的对手散装纳米材料可能有额外的危害。 1.摄政的制备制备通过溶解0.0012克1,1'-二甲基-4,4'-双吡啶鎓二氯化物的甲基紫精的水溶液;在20毫升水中，得到0.2mM的MV 2+（甲基紫精的MV 2+）。 通过在10毫升的水0.1050克金（Ⅲ）四氯化三水合物（?…
Representative Results
两种类型的前体薄膜在该研究中使用（ 即，具有和不具有所述保护试剂（2-AET +）TNS的夹层内）。在没有2-AET +，1,1'-二甲基-4,4'-双吡啶鎓二氯化物（甲基紫精; MV 2+）作为中间层的空间的膨胀，因为MV 2+含LMOSs已经常用作在来宾交换方法的中间体用于制备LMOSs 16,17,21,33-36。 金纳?…
Discussion
这个手稿提供了原位合成TNS膜的层间空间内金粒子（AuNPs）的详细协议。这是在原位合成TNS的层间空间内金纳米粒子的第一份报告。此外，我们发现，2-AET +作品作为TNS的夹层内的AuNPs有效的保护试剂。这些方法杂交金纳米粒子和TNS透明薄膜。 TNS膜具有良好的光学透明性21是通过烧结工艺（S-TNS膜）合成，如在协议部分呈现。烧结过程重复所需的完全除去有机杂质。当?…
Declarações
The authors have nothing to disclose.
Acknowledgements
This work was partly supported by Nippon Sheet Glass Foundation for Materials Science and Engineering and JSPS KAKENHI (Grant-in-Aid for Challenging Exploratory Research, #50362281).
Materials
| Methyl viologen dichloride | Aldrich Chemical Co., Inc. | 1910-42-5 | |
| Tetrabutylammonium hydroxide | TCI | T1685 | |
| cesium carbonate | Kanto Chemical Co., Inc. | 07184-33 | |
| anatase titanium dixoide | Ishihara Sangyo Ltd. | ST-01 | |
| hydrochloric acid | Junsei Chemical Co., Ltd. | 20010-0350 | |
| sodium hydroxide | Junsei Chemical Co., Ltd. | 195-13775 | |
| Tetrachloroauric(III) acid trihydrate | Kanto Chemical Co., Inc. | 17044-60 | |
| sodium tetrahydroborate | Junsei Chemical Co., Ltd. | 39245-1210 | |
| 2-ammoniumethanethiol hydrochloride | TCI | A0296 | |
| Ultrapure water (0.056 µS/cm) | Milli-Q water purification system (Direct-Q® 3UV, Millipore) | ||
| Microscope slide (Thickness : 1.0∼1.2 mm) | Matsunami glass Co., Ltd. | ||
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Citar este artigo
Sasaki, K., Matsubara, K., Kawamura, S., Saito, K., Yagi, M., Yui, T. In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films. J. Vis. Exp. (119), e55169, doi:10.3791/55169 (2017).