Summary

層状チタン酸透明フィルムの層間空間で凝集することなく金ナノ粒子のその場合成

Published: January 17, 2017
doi:

Summary

ここでは、AuNPsの凝集せず、層状チタン酸膜の層間空間内の金ナノ粒子(AuNPs)のin situ合成のためのプロトコルを提示します。いいえスペクトル変化はあっても4ヶ月後には観察されませんでした。合成された材料は、触媒、光触媒、及び費用対効果プラズモンデバイスの開発への応用が期待されています。

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

種々の貴金属ナノ粒子(MNPの)は、それらの局在表面プラズモン共鳴(LSPR)特性に特徴色または色調を呈します。従って、のMNPは、様々な光学的および/または光化学用途1-4で使用することができます。最近、金属酸化物半導体(MOS)は、酸化チタン(TiO 2)とのMNPのような光触媒の組み合わせは、十分に光触媒5-14の新しいタイプとして研究されてきました。ほとんどのMOS粒子は、比較的低い表面積を有するしかし、多くの場合、のMNPの非常に少量が、MOSの表面上に存在します。一方、層状金属酸化物半導体(LMOSs)光触媒特性を示し、大きな表面積を有し、LMOS 15-17の単位グラム当たり典型的には数百平方メートル。さらに、様々なLMOSsは、インターカレーション特性( すなわち、種々の化学種が、その拡張可能と大きな層間空間内に収容することができる)15-20を有します。したがって、のMNP及びLMOSsの組み合わせで、それのMNP比較的大量の半導体光触媒とハイブリダイズさせることが期待されます。

非常に単純な工程を経て透明フィルム;私たちは、LMOSの層間空間内の銅ナノ粒子(CuNPs)21その場合成の最初 (TNS 16-30チタニアナノシート)を報告しています。しかし、合成手順の詳細、および他の貴族のMNPとTNSハイブリッドの特性はまだ報告されていません。また、TNS層内CuNPsは容易に酸化し、周囲条件下21の下で脱色しました。このように、我々はAuNPsが広く、様々な光学的、光化学的に使用されているため、金ナノ粒子(AuNPs)に着目し、触媒用途、それらが酸化に対して比較的安定であることが予想される3-5,7,8,10-14 、28,31,32。ここでは、TNSおよびshow股関節の層間空間内AuNPsの合成を報告しますトン2-ammoniumethanethiol(2-AET +; 図1挿入図)は、TNSの層間内AuNPsの保護試薬として有効に働きます。

Protocol

注意:化学物質やソリューションを扱うときに常に注意してください。適切な安全対策に従ってください、常に手袋、眼鏡、と白衣を着用してください。ナノ材料は、それらのバルクの対応と比較して付加的な危険性を有していてもよいことに注意してください。 リージェンツの調製 0.2 mMのMV 2+を与えるために水20mlに、1,1'-ジメチル-4,4'-ビピリジニウムジクロリド…

Representative Results

前駆体フィルムの二つのタイプ( すなわち、とし、TNSの層間内に保護試薬(2-AET +)なしで)、本研究で使用しました。 2-AET +の非存在下では、1,1'-ジメチル-4,4'-ビピリジニウムジクロリド(メチルビオロゲン、MV 2+)MV 2+含有LMOSsがされているので、中間領域のエクスパンダとして使用されました頻繁にLMOSs 16,17,21,33-36?…

Discussion

この原稿は、TNSフィルムの層間空間内の金ナノ粒子(AuNPs)のin situ合成のための詳細なプロトコルを提供します。これは、TNSの層間空間内AuNPsのin situ合成の最初の報告です。さらに、我々は2-AET +は、TNSの層間内AuNPsのための有効な保護試薬として機能することがわかりました。これらのメソッドはAuNPsとTNS透明フィルムをハイブリダイズしました。プロトコルセクション…

Disclosures

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.

References

  1. Kelly, K. L., Coronado, E., Zhao, L. L., Schatz, G. C. The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment. J. Phys. Chem. B. 107 (3), 668-677 (2003).
  2. Rycenga, M., et al. Controlling the Synthesis and Assembly of Silver Nanostructures for Plasmonic Applications. Chem. Rev. 111 (6), 3669-3712 (2011).
  3. The Binh, N., et al. Preparation of metal nanoparticles for surface enhanced Raman scattering by laser ablation method. Adv. Nat. Sci.: Nanosci. Nanotechnol. 3 (2), 025016 (2012).
  4. Chen, H., Shao, L., Li, Q., Wang, J. Gold nanorods and their plasmonic properties. Chem. Soc. Rev. 42 (7), 2679-2724 (2013).
  5. Subramanian, V., Wolf, E. E., Kamat, P. V. Influence of Metal/Metal Ion Concentration on the Photocatalytic Activity of TiO2-Au Composite Nanoparticles. Langmuir. 19 (2), 469-474 (2003).
  6. Linic, S., Christopher, P., Ingram, D. B. Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy. Nat Mater. 10 (12), 911-921 (2011).
  7. Gomes Silva, C., Juárez, R., Marino, T., Molinari, R., García, H. Influence of Excitation Wavelength (UV or Visible Light) on the Photocatalytic Activity of Titania Containing Gold Nanoparticles for the Generation of Hydrogen or Oxygen from Water. J. Am. Chem. Soc. 133 (3), 595-602 (2011).
  8. Hou, W., et al. Photocatalytic Conversion of CO2 to Hydrocarbon Fuels via Plasmon-Enhanced Absorption and Metallic Interband Transitions. ACS Catal. 1 (8), 929-936 (2011).
  9. Wang, W. -. N., et al. Size and Structure Matter: Enhanced CO2 Photoreduction Efficiency by Size-Resolved Ultrafine Pt Nanoparticles on TiO2 Single Crystals. J. Am. Chem. Soc. 134 (27), 11276-11281 (2012).
  10. Shi, X., Ueno, K., Takabayashi, N., Misawa, H. Plasmon-Enhanced Photocurrent Generation and Water Oxidation with a Gold Nanoisland-Loaded Titanium Dioxide Photoelectrode. J. Phys. Chem. C. 117 (6), 2494-2499 (2013).
  11. Tanaka, A., Sakaguchi, S., Hashimoto, K., Kominami, H. Preparation of Au/TiO2 with Metal Cocatalysts Exhibiting Strong Surface Plasmon Resonance Effective for Photoinduced Hydrogen Formation under Irradiation of Visible Light. ACS Catal. 3 (1), 79-85 (2013).
  12. Bian, Z., Tachikawa, T., Zhang, P., Fujitsuka, M., Majima, T. Au/TiO2 Superstructure-Based Plasmonic Photocatalysts Exhibiting Efficient Charge Separation and Unprecedented Activity. J. Am. Chem. Soc. 136 (1), 458-465 (2014).
  13. Ide, Y., et al. Hybridization of Au nanoparticle-loaded TiO2 with BN nanosheets for efficient solar-driven photocatalysis. J. Mater. Chem. A. 2 (12), 4150-4156 (2014).
  14. Zheng, Z., Tachikawa, T., Majima, T. Plasmon-induced spatial electron transfer between single Au nanorods and ALD-coated TiO2: dependence on TiO2 thickness. Chem. Commun. 51 (76), 14373-14376 (2015).
  15. Inui, Y., et al. Reversible redox processes of poly(anilines) in layered semiconductor niobate films under alternate UV-Vis light illumination. J. Phys. Chem. B. 111 (42), 12162-12169 (2007).
  16. Yui, T., Takagi, K., Ariga, K., Nalwa, H. S. . Bottom-up Nanofabrication Vol. 5. 5, 35-90 (2009).
  17. Sasai, R., Yui, T., Takagi, K., Nalwa, H. S. . Encyclopedia of Nanoscience and Nanotechnology Vol. 24. , 303-361 (2011).
  18. Yui, T., et al. Visible light-induced electron transfers in titania nanosheet and mesoporous silica integrated films. Bull. Chem. Soc. Jpn. 79 (3), 386-396 (2006).
  19. Yui, T., et al. Photoinduced one-electron reduction of MV2+ in titania nanosheets using porphyrin in mesoporous silica thin films. Langmuir. 21 (7), 2644-2646 (2005).
  20. Yui, T., et al. Remarkably stabilized charge separations in inorganic nanospace. Bull. Chem. Soc. Jpn. 82 (7), 914-916 (2009).
  21. Sasaki, K., et al. Synthesis of copper nanoparticles within the interlayer space of titania nanosheet transparent films. J. Mater. Chem. C. 4 (7), 1476-1481 (2016).
  22. Sasaki, T., Komatsu, Y., Fujiki, Y. A new layered hydrous titanium dioxide HTi2 -/4O4[middle dot]H2O. J. Chem. Soc., Chem. Commun. (12), 817-818 (1991).
  23. Sasaki, T., Watanabe, M. Osmotic Swelling to Exfoliation. Exceptionally High Degrees of Hydration of a Layered Titanate. J. Am. Chem. Soc. 120 (19), 4682-4689 (1998).
  24. Yui, T., et al. Synthesis of photofunctional titania nanosheets by electrophoretic deposition. Chem. Mater. 17 (1), 206-211 (2005).
  25. Tachikawa, T., Yui, T., Fujitsuka, M., Takagi, K., Majima, T. Photocatalytic electron transfer in hybrid titania nanosheets studied by nanosecond laser flash photolysis. Chem. Lett. 34 (11), 1522-1523 (2005).
  26. Zhou, Y., Ma, R., Ebina, Y., Takada, K., Sasaki, T. Multilayer Hybrid Films of Titania Semiconductor Nanosheet and Silver Metal Fabricated via Layer-by-Layer Self-Assembly and Subsequent UV Irradiation. Chem. Mater. 18 (5), 1235-1239 (2006).
  27. Yui, T., et al. Photochemical electron transfer though the interface of hybrid films of titania nano-sheets and mono-dispersed spherical mesoporous silica particles. Phys. Chem. Chem. Phys. 8 (39), 4585-4590 (2006).
  28. Sakai, N., Sasaki, T., Matsubara, K., Tatsuma, T. Layer-by-layer assembly of gold nanoparticles with titania nanosheets: control of plasmon resonance and photovoltaic properties. J. Mater. Chem. 20 (21), 4371-4378 (2010).
  29. Yui, T., et al. Photoinduced Electron Transfer between the Anionic Porphyrins and Viologens in Titania Nanosheets and Monodisperse Mesoporous Silica Hybrid Films. ACS Appl. Mater. Interfaces. 3 (4), 931-935 (2011).
  30. Wang, L., Sasaki, T. Titanium Oxide Nanosheets: Graphene Analogues with Versatile Functionalities. Chem. Rev. 114 (19), 9455-9486 (2014).
  31. Eguchi, M., Ito, M., Ishibashi, T. -. a. Stabilization and Modification of Gold Nanocube Surfaces with Layered Silicate. Chem. Lett. 43 (1), 140-142 (2014).
  32. Fujimura, T., Yoshida, Y., Inoue, H., Shimada, T., Takagi, S. Dense Deposition of Gold Nanoclusters Utilizing a Porphyrin/Inorganic Layered Material Complex as the Template. Langmuir. 31 (33), 9142-9147 (2015).
  33. Tong, Z., Shichi, T., Takagi, K. Visible-Light Induced Charge-Separation between Consecutively Cast Porphyrin and Methyl Viologen Multilayered Titanoniobate Hybrid Films. J. Phys. Chem. B. 106 (51), 13306-13310 (2002).
  34. Tong, Z., Shichi, T., Oshika, K., Takagi, K. A Nanostructured Hybrid Material Synthesized by the Intercalation of Porphyrin into Layered Titanoniobate. Chem. Lett. 31 (9), 876-877 (2002).
  35. Tong, Z., Takagi, S., Tachibana, H., Takagi, K., Inoue, H. Novel Soft Chemical Method for Optically Transparent Ru(bpy)3-K4Nb6O17 Thin Film. J. Phys. Chem. B. 109 (46), 21612-21617 (2005).
  36. Hattori, T., et al. Hybridization of layered niobates with cationic dyes. Res. Chem. Intermed. 32 (7), 653-669 (2006).
  37. Moreau, F., Bond, G. C., Taylor, A. O. Gold on titania catalysts for the oxidation of carbon monoxide: control of pH during preparation with various gold contents. J. Catal. 231 (1), 105-114 (2005).
  38. Ivanova, S., Petit, C., Pitchon, V. A new preparation method for the formation of gold nanoparticles on an oxide support. Appl. Cat. A. 267 (1-2), 191-201 (2004).
  39. Sasaki, T., Watanabe, M., Hashizume, H., Yamada, H., Nakazawa, H. Macromolecule-like Aspects for a Colloidal Suspension of an Exfoliated Titanate. Pairwise Association of Nanosheets and Dynamic Reassembling Process Initiated from It. J. Am. Chem. Soc. 118 (35), 8329-8335 (1996).
  40. Tanaka, T., Ebina, Y., Takada, K., Kurashima, K., Sasaki, T. Oversized Titania Nanosheet Crystallites Derived from Flux-Grown Layered Titanate Single Crystals. Chem. Mater. 15 (18), 3564-3568 (2003).
  41. . . Denkikagaku Binran, 5th edn. , (2000).
  42. Shannon, R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst. 32, 751-767 (1976).
  43. Jia, Y. Q. Crystal radii and effective ionic radii of the rare earth ions. J. Solid State Chem. 95 (1), 184-187 (1991).
  44. Grabar, K. C., Freeman, R. G., Hommer, M. B., Natan, M. J. Preparation and Characterization of Au Colloid Monolayers. Anal. Chem. 67 (4), 735-743 (1995).
  45. Niidome, T., Nakashima, K., Takahashi, H., Niidome, Y. Preparation of primary amine-modified gold nanoparticles and their transfection ability into cultivated cells. Chem. Commun. (17), 1978-1979 (2004).
  46. Kawano, T., Horiguchi, Y., Niidome, Y., Niidome, T., Yamada, S. Preparation of Cationic Gold Nanoparticle in Aqueous Solutions of 2-Aminoethanethiol Hydrochloride. Bunseki Kagaku. 54 (6), 521-526 (2005).
  47. Tong, Z., Shichi, T., Kasuga, Y., Takagi, K. The Synthesis of Two Types of Layered Niobate Hybrid Materials by the Selective Intercalation of Ionic Porphyrin. Chem. Lett. 31 (12), 1206-1207 (2002).
  48. Zhao, S., Chen, S., Wang, S., Quan, Z. Composite Au/TiO2 Nanoparticles: Synthesis, Characterization, and Assembly by Using Potentiostatic Technique. J. Colloid Interface Sci. 221 (2), 161-165 (2000).
  49. Negishi, Y., Nobusada, K., Tsukuda, T. Glutathione-Protected Gold Clusters Revisited: Bridging the Gap between Gold(I)-Thiolate Complexes and Thiolate-Protected Gold Nanocrystals. J. Am. Chem. Soc. 127 (14), 5261-5270 (2005).
  50. Schmidt-Stein, F., et al. X-ray induced photocatalysis on TiO2 and TiO2 nanotubes: Degradation of organics and drug release. Electrochem. Commun. 11 (11), 2077-2080 (2009).
  51. Tamura, K., et al. X-ray induced photoelectrochemistry on TiO2. Electrochim. Acta. 52 (24), 6938-6942 (2007).

Play Video

Cite This Article
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).

View Video