Mesoporous silica nanoparticles (MSNs) are experiencing rapid development in the biomedical field for imaging and for use in heterogeneous catalysis. Although the synthesis of MSNs with various morphologies and particle sizes has been reported, synthesis of a pore network with monodispersion control below 200 nm is still challenging. We achieved this goal using mild conditions. The reaction occurred at atmospheric pressure with a templating sol-gel technique using cetyltrimethylammonium (CTA(+)) as the templating surfactant and small organic amines (SOAs) as the mineralizing agent. Production of small pore sizes was performed for the first time, using pure and redispersible monodispersed porous nanophases with either stellate (ST) or raspberry-like (RB) channel morphologies. Tosylate (Tos(-)) counterions favored ST and bromide (Br(-)) RB morphologies at ultralow SOA concentrations. Both anions yielded a worm-like (WO) morphology at high SOA concentrations. A three-step formation mechanism based on self-assembly and ion competition at the electrical palisade of micelles is proposed. Facile recovery and redispersion using specific SOAs allowed a high yield production at the kilogram scale. This novel technique has practical applications in industry.
Nanosized Beta zeolites were postsynthetically modi-fied through the solid−gas reaction of highly dealuminated Beta zeolite with SnCl4 vapor at elevated temperatures. The incorporation mechanism of Sn ions and the physicochemical properties of resultant Sn-Beta-PS were characterized by various techniques. Its catalytic performance in Baeyer−Villiger oxidation was compared with the micrometer-sized Sn-Beta-F hydrothermally synthesized by conventional fluoride method. The Sn species were inserted into the framework via the reaction of the SnCl4 molecules with the silanols in the hydroxyl nests that were created by dealumination and thus occupied predominately the tetrahedral coordination sites. The Sn content gained by postsynthesis reached up to 6.2 wt %, corresponding to a Si/Sn ratio of ca. 35. The isolated Sn species exhibited Lewis acidity useful for the Baeyer−Villiger oxidation of ketones. Containing higher Sn contents and more importantly proposing less diffusion limitations to the substrates with a large molecular dimension, nanosized Sn-Beta-PS was superior to Sn-Beta-F in the selective oxidation of 2-adamantanone with hydrogen peroxide.
Recently, metal nanoclusters (MNCs) emerged as a new class of luminescent materials and have attracted tremendous interest in the area of luminescence-related applications due to their excellent luminous properties (good photostability, large Stokes shift) and inherent good biocompatibility. However, the origin of photoluminescence (PL) of MNCs is still not fully understood, which has limited their practical application. In this mini-review, focusing on the origin of the photoemission emission of MNCs, we simply review the evolution of luminescent mechanism models of MNCs, from the pure metal-centered quantum confinement mechanics to ligand-centered p band intermediate state (PBIS) model via a transitional ligand-to-metal charge transfer (LMCT or LMMCT) mechanism as a compromise model.
Germanosilicates, an important family of zeolites with increasing number of members and attractive porosities, but containing a large quantity of unstable Ge atoms in the framework, meet with great obstacles in terms of limited thermal and hydrothermal stability when it comes to practical use. A facile stabilization method thus has been developed to substitute isomorphously Ge atoms for Si atoms, giving rise to ultrastable siliceous analogues of the pristine germanosilicates.
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