In situ Síntese de Nanopartículas de Ouro sem agregação no espaço Interlayer de Layered titanato filmes transparentes
Summary
Aqui, apresentamos um protocolo para a in situ síntese de nanopartículas de ouro (AuNPs) dentro do espaço interlamelar de filmes de titanato de camadas sem a agregação de AuNPs. Nenhuma mudança foi observada espectral mesmo após 4 meses. O material sintetizado tem esperado aplicações em catálise, foto-catálise, e para o desenvolvimento de dispositivos plasmonic rentáveis.
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
Vários nanopartículas de metais nobres (MNPS) exibem cores características ou tons devido à sua ressonância de plasma de superfície localizada propriedades (LECC); Assim, MNPs pode ser usado em várias aplicações ópticas e / ou fotoquímicos 1-4. Recentemente, combinações de fotocatalisadores semicondutores de óxido metálico (MOS), tal como óxido de titânio (TiO 2) e MNPs, foram cuidadosamente investigados como novos tipos de fotocatalisadores 5-14. No entanto, em muitos casos, existem quantidades muito pequenas de MNPs na superfície do MOS, porque a maioria das partículas têm áreas de superfície MOS relativamente baixas. Por outro lado, os semicondutores de óxido de metal em camadas (LMOSs) exibem propriedades foto catalíticas e ter uma grande área superficial, tipicamente, várias centenas de metros quadrados por unidade de g de um LMOS 15-17. Além disso, vários LMOSs têm propriedades de intercalação (por exemplo, várias espécies químicas podem ser acomodados dentro dos seus espaços intercamada expansíveis e grandes) 15-20. Assim, com uma combinação de MNPS e LMOSs, espera-se que quantidades relativamente grandes de MNPs são hibridados com os fotocatalisadores semicondutores.
Nós relatamos o primeiro na síntese in situ de nanopartículas de cobre (CuNPs) 21 dentro do espaço intercalar de OVMs (titânia nanosheet; TNS 16-30) filmes transparentes através de passos muito simples. No entanto, os detalhes dos procedimentos de síntese e a caracterização dos outros híbridos MnPs e TNS nobres ainda não foram relatados. Além disso, os CuNPs dentro das camadas TNS foram facilmente oxidados e descorou-se sob as condições ambientes 21. Como tal, nós nos concentramos em nanopartículas de ouro (AuNPs), porque AuNPs são amplamente utilizados para vários óptica, fotoquímica e aplicações catalíticas, e espera-se que eles vão ser relativamente estável contra a oxidação 3-5,7,8,10-14 , 28,31,32. Aqui, nós relatamos a síntese de AuNPs dentro do espaço intercalar da TNS e mostrar that 2-ammoniumethanethiol (2-AET +; Figura 1 inserção) funciona eficazmente como um reagente de protecção para AuNPs dentro do intercalar da TNS.
Protocol
Representative Results
Discussion
Este manuscrito proporciona um protocolo detalhado para a síntese in situ de nanoparticulas de ouro (AuNPs) dentro do espaço interlamelar de filmes TNS. Este é o primeiro relatório do in situ síntese de AuNPs dentro do espaço intercalar da TNS. Além disso, descobrimos que o 2-AET + funciona como um reagente de protecção eficaz para AuNPs dentro do intercalar da TNS. Estes métodos hybridized AuNPs e TNS filmes transparentes. Filmes TNS com boa transparência óptica 21 fo…
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. | ||
Referências
- 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).
- Rycenga, M., et al. Controlling the Synthesis and Assembly of Silver Nanostructures for Plasmonic Applications. Chem. Rev. 111 (6), 3669-3712 (2011).
- 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).
- Chen, H., Shao, L., Li, Q., Wang, J. Gold nanorods and their plasmonic properties. Chem. Soc. Rev. 42 (7), 2679-2724 (2013).
- 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).
- 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).
- 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).
- 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).
- 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).
- 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).
- 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).
- 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).
- 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).
- 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).
- 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).
- Yui, T., Takagi, K., Ariga, K., Nalwa, H. S. . Bottom-up Nanofabrication Vol. 5. 5, 35-90 (2009).
- Sasai, R., Yui, T., Takagi, K., Nalwa, H. S. . Encyclopedia of Nanoscience and Nanotechnology Vol. 24. , 303-361 (2011).
- 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).
- 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).
- Yui, T., et al. Remarkably stabilized charge separations in inorganic nanospace. Bull. Chem. Soc. Jpn. 82 (7), 914-916 (2009).
- 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).
- 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).
- 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).
- Yui, T., et al. Synthesis of photofunctional titania nanosheets by electrophoretic deposition. Chem. Mater. 17 (1), 206-211 (2005).
- 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).
- 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).
- 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).
- 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).
- 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).
- Wang, L., Sasaki, T. Titanium Oxide Nanosheets: Graphene Analogues with Versatile Functionalities. Chem. Rev. 114 (19), 9455-9486 (2014).
- Eguchi, M., Ito, M., Ishibashi, T. -. a. Stabilization and Modification of Gold Nanocube Surfaces with Layered Silicate. Chem. Lett. 43 (1), 140-142 (2014).
- 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).
- 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).
- 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).
- 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).
- Hattori, T., et al. Hybridization of layered niobates with cationic dyes. Res. Chem. Intermed. 32 (7), 653-669 (2006).
- 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).
- 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).
- 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).
- 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).
- . . Denkikagaku Binran, 5th edn. , (2000).
- Shannon, R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst. 32, 751-767 (1976).
- Jia, Y. Q. Crystal radii and effective ionic radii of the rare earth ions. J. Solid State Chem. 95 (1), 184-187 (1991).
- 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).
- 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).
- 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).
- 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).
- 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).
- 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).
- 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).
- Tamura, K., et al. X-ray induced photoelectrochemistry on TiO2. Electrochim. Acta. 52 (24), 6938-6942 (2007).
