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Visible Light Catalysis-Assisted Assembly of NihQD Hollow Nanospheres in situ via Hydrogen Bubbles
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Update time: 2014-05-20
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Hollow spheres are one of the most promising micro/nanostructures because of their unique performance in diverse applications. Templates, surfactants, and structure-directing agents are often used to control the sizes and morphologies of hollow spheres. In this report, we describe a simple method based on visible light catalysis for preparing hollow nanospheres from CdE (E = Te, Se, and S) quantum dots (QDs) and nickel (Ni2+) salts in aqueous media. In contrast to the well-developed traditional approaches, the hollow nanospheres of QDs are formed in situ by the photogeneration of hydrogen (H2) gas bubbles at room temperature. Each component, i.e., the QDs, metal ions, ascorbic acid (H2A), and visible light, is essential for the formation of hollow nanospheres. The quality of the hollow nanospheres depends on the pH, metal ions, and wavelength and intensity of visible light used. Of the various metal ions investigated, including Cu+, Cu2+, Fe2+, Fe3+, Ni2+, Mn2+, RuCl52-, Ag+, and PtCl42-, Ni2+ ions showed the best ability to generate H2 and hollow-structured nanospheres under visible light irradiation. The average diameter and shell thickness of the nanospheres ranged from 10-20 nm and from 3-6 nm, respectively, which are values rarely reported in the literature. Studies using high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), inductively coupled plasma-mass spectroscopy (ICP-AES), and steady-state and time-resolved spectroscopy revealed the chemical nature of the hollow nanospheres. Additionally, the hollow-structured nanospheres exhibit excellent photocatalytic activity and stability for the generation of H2 with a rate constant of 21 μmol h-1 mg-1 and a turnover number (TON) of 137 500 or 30 250 for CdTe QDs or nickel, respectively, under visible light irradiation for 42 h.
Journal of the American Chemical Society, 2014
HRTEM images of Nih-CdTe hollow nanospheres (a-bc) (scale bars: a 100 nm, b 20 nm, c 10 nm), and their SAED pattern (e) with three diffraction rings; HRTEM image of the 
MPA-CdTe QDs (d), and their SAED pattern (f) with three diffraction rings.
HRTEM images of hollow Nih-CdTe nanospheres obtained at different pH values (scale bar: 10 nm).
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