We report the first observation of band gap chemiluminescence of semiconductor quantum dots in solution and in nanoparticulate layers. The spectral position of the band gap chemiluminescence of CdSe/CdS core shell and InP nanocrystals depends on their particle size, allowing thus an efficient tuning of the emission color with superior color purity inherent for monodisperse samples. The efficiency of nanocrystal chemiluminescence can be dramatically enhanced by applying a cathodic potential to the nanoparticulate layers made from CdSe or CdSe/ CdS core−shell nanocrystals. In this case electrochemical n-doping of the particles via electron injection provides a "quantum confined cathodic protection" against nanocrystal oxidative corrosion upon hole injection and allows the achievement of efficient and stable electrogenerated chemiluminescence.
Zn-Al and Mg-Al layered double hydroxides (LDHs) loaded with quinaldate and 2-mercaptobenzothiazolate anions were synthesized via anion-exchange reaction. The resulting compounds were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy/energy-dispersive X-ray spectroscopy. Spectrophotometric measurements demonstrated that the release of organic anions from these LDHs into the bulk solution is triggered by the presence of chloride anions, evidencing the anion-exchange nature of this process. The anticorrosion capabilities of LDHs loaded with organic inhibitors toward the AA2024 aluminum alloy were analyzed by electrochemical impedance spectroscopy. A significant reduction of the corrosion rate is observed when the LDH nanopigments are present in the corrosive media. The mechanism by which the inhibiting anions can be released from the LDHs underlines the versatility of these environmentally friendly structures and their potential application as nanocontainers in self-healing coatings.
Electrochemical studies of thiol-capped CdTe nanocrystals in aqueous solution have demonstrated several distinct oxidation and reduction peaks in the voltammograms, with the peak positions being dependent on the size of the nanocrystals. While the size dependence of the reduction and one of the oxidation potentials can be attributed to altering the energetic band positions owing to the quantum size effect, an extraordinary behavior was found for the oxidation peak observed at less positive potentials. In contrast to a prediction based on the quantum size effect, this peak moves to more negative potentials as the nanocrystals' size decreases. Moreover, the contribution of the charge associated with this peak compared to the total charge passed during the nanocrystal oxidation correlates well with the photoluminescence (PL) efficiency of individual fractions of the CdTe nanocrystals. These experimental observations allow a peak to be assigned to the oxidation of Te-related surface traps. The intra-band-gap energy level assigned to these Te-related trap states shifts toward the top of the valence band as the nanocrystal size increases, thus allowing the higher photostability of the larger nanocrystals to be explained. At a certain nanocrystal size, the trap level can even move out of the band gap.
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