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羟基自由基(OH)在极端pH条件下高选择性金纳米线形成中的作用:金纳米线催化还原反应速率的多重增强。

The role of OH in the formation of highly selective gold nanowires at extreme pH: multi-fold enhancement in the rate of the catalytic reduction reaction by gold nanowires.

作者信息

El Kurdi Riham, Patra Digambara

机构信息

Department of Chemistry, American University of Beirut, Beirut, Lebanon.

出版信息

Phys Chem Chem Phys. 2017 Feb 15;19(7):5077-5090. doi: 10.1039/c6cp08607a.

DOI:10.1039/c6cp08607a
PMID:28134362
Abstract

There is a quest to understand the mechanism governing the morphology and geometry control of the particle growth of nanomaterials for their optical and catalytic applications. In the available literature, the role of OH in dictating the size and shape of Au nanowires is unknown. As one of the first examples, herein, we explore how excess OH ions in CTAB micelles play a significant role during the highly selective formation of gold nanowires having controlled diameters of ∼20-25 nm and length >1 μm, by reducing Au to Au in a one pot, simple synthesis procedure in the presence of Ag ions. At pH 4-11, the same procedure does not harvest Au NWs, but Au NPs of diameter 50-70 nm, indicating that excess OH is needed for nanowire formation. XRD, TGA, DSC, EDX, FT-IR and fluorescence spectroscopic analysis confirm that both CTAB and curcumin act as capping and stabilizing agents for Au NWs as well as Au NPs - there is no remarkable difference in the curcumin/CTAB content between Au NWs and NPs prepared in different pH environments. However, changing the CTAB micellar media to DPPC liposome media inhibits the formation of nanowires at pH ∼13; the growth of the Au NPs diminishes in DPPC liposomes, offering smaller NPs of diameter ∼25 to 30 nm, suggesting that the role of CTAB is necessary in nanowire formation. The rate of NW formation has been found to be 0.13 h and the growth mechanism advocates elongation in the [110] facet of Au [110] as opposed to the [100] or [111] facets. Curcumin capped Au nanowires serve as excellent nano-catalysts for the reduction of nitro-compounds and the rate of reduction of 4-nitrophenol, a model compound, by curcumin capped Au NWs is found to be ∼10 fold higher, compared to Au NPs, which signifies that catalytic activities can be dictated by the size and shape of Au NPs.

摘要

人们一直在探索控制纳米材料颗粒生长的形态和几何结构的机制,以用于光学和催化应用。在现有文献中,OH在决定金纳米线尺寸和形状方面的作用尚不清楚。作为首批实例之一,本文中我们探究了在CTAB胶束中过量的OH离子如何在有Ag离子存在的情况下,通过一锅简单合成法将Au还原为Au,从而在高度选择性地形成直径约20 - 25 nm且长度大于1μm的金纳米线过程中发挥重要作用。在pH 4 - 11时,相同的方法无法得到金纳米线,而是得到直径为50 - 70 nm的金纳米颗粒,这表明纳米线的形成需要过量的OH。XRD、TGA、DSC、EDX、FT - IR和荧光光谱分析证实,CTAB和姜黄素均作为金纳米线以及金纳米颗粒的封端和稳定剂——在不同pH环境下制备的金纳米线和金纳米颗粒之间,姜黄素/CTAB的含量没有显著差异。然而,将CTAB胶束介质换成DPPC脂质体介质会在pH约为13时抑制纳米线的形成;在DPPC脂质体中,金纳米颗粒的生长减弱,得到直径约25至30 nm的较小纳米颗粒,这表明CTAB在纳米线形成中起着必要作用。已发现纳米线的形成速率为0.13 h,其生长机制主张在金[110]的[110]晶面上伸长,而非在[100]或[111]晶面上。姜黄素封端的金纳米线是还原硝基化合物的优良纳米催化剂,与金纳米颗粒相比,姜黄素封端的金纳米线对模型化合物4 - 硝基苯酚的还原速率高出约10倍,这表明催化活性可由金纳米颗粒的尺寸和形状决定。

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