Water-dispersible ZnS:Mn nanocrystals (NC) were synthesized by capping the surface with mercaptoacetic acid (MAA) molecules at three different pH conditions. The obtained ZnS:Mn-MAA NC products were physically and optically characterized by corresponding spectroscopic methods. The UV-Visible absorption spectra and PL emission spectra showed broad peaks at 310 and 590 nm, respectively. The average particle sizes measured from the HR-TEM images were 5 nm, which were also supported by the Debye-Scherrer calculations using the X-ray diffraction (XRD) data. Moreover, the surface charges and the degrees of aggregation of the ZnS:Mn-MAA NCs were determined by electrophoretic and hydrodynamic light scattering methods, indicating formation of agglomerates in water with various sizes (50–440 nm) and different surface charge values accordingly the preparation conditions of the NCs (−7.59 to −24.98 mV). Finally, the relative photocatalytic activities of the ZnS:Mn-MAA NCs were evaluated by measuring the degradation rate of methylene blue (MB) molecule in a pseudo first-order reaction condition under the UV-visible light irradiation. As a result, the ZnS:Mn-MAA NC prepared at the pH 7 showed the best photo-degradation efficiency of the MB molecule with the first-order rate constant (kobs) of 2.0 × 10−3·min−1.
Water-dispersible ZnS:Mn nanocrystals (NCs) were synthesized by capping the surface with polar L-aspartic acid (Asp) molecules. The obtained ZnS:Mn-Asp NC product was optically and physically characterized using the corresponding spectroscopic methods. The ultra violet-visible (UV-VIS) absorption spectrum and photoluminescence (PL) emission spectrum of the NCs showed broad peaks at 320 and 590 nm, respectively. The average particle size measured from the obtained high resolution-transmission electron microscopy (HR-TEM) image was 5.25 nm, which was also in accordance with the Debye-Scherrer calculations using the X-ray diffraction (XRD) data. Moreover, the surface charge and degree of aggregation of the ZnS:Mn-Asp NCs were determined by electrophoretic and hydrodynamic light scattering methods, respectively. These results indicated the formation of agglomerates in water with an average size of 19.8 nm, and a negative surface charge (−4.58 mV) in water at ambient temperature. The negatively-charged NCs were applied as a photosensor for the detection of specific cations in aqueous solution. Accordingly, the ZnS:Mn-Asp NCs showed an exclusive luminescence quenching upon addition of copper (II) cations. The kinetic mechanism study on the luminescence quenching of the NCs by the addition of the Cu2+ ions proposed an energy transfer through the ionic binding between the two oppositely-charged ZnS:Mn-Asp NCs and Cu2+ ions.
20 January 2013 in Bulletin of the Korean Chemical Society
Water-dispersible ZnS:Mn nanoparticles (NPs) were prepared by capping their surface with simple structured amino acids: l-alanine (Ala), l-glycine (Gly), and l-valine (Val) molecules, which have very similar structures except for the terminal organic functional groups. The detailed characterization works for the prepared colloidal NPs were performed using various spectroscopic methods. In particular, the NPs commonly showed UV/visible absorption peaks around 325 nm and PL emission peaks around 590 nm, corresponding to the wavelength of orange color light. In this study, these amino-acid-capped NPs were applied as optical photosensors in the detection of specific divalent transition metal cations in the same conditions. Consequently, all three NPs showed exclusive fluorescence quenching effects upon the addition of Cu (II) metal ions, whereas their quenching efficiencies were quite different to each other. These experimental results indicated that the Gly-ZnS:Mn NPs (k = 4.09 × 105 M−1) can be the most effective optical photosensor for the detection of Cu2+ ions in water among the three NPs in the same conditions. This study showed that the steric effect of the capping ligand can be one of the key factors affecting the sensor activities of the ZnS:Mn NPs.
20 January 2014 in Bulletin of the Korean Chemical Society