RESUMEN
There is growing evidence for the advantages of synthesizing nanosized zeolites with markedly reduced internal diffusion limitations for enhanced performances in catalysis and adsorption. Producing zeolite crystals with sizes less than 100 nm, however, is non-trivial, often requires the use of complex organics and typically results in a small product yield. Here we present an alternative, facile approach to enhance the mass-transport properties of zeolites by the epitaxial growth of fin-like protrusions on seed crystals. We validate this generalizable methodology on two common zeolites and confirm that fins are in crystallographic registry with the underlying seeds, and that secondary growth does not impede access to the micropores. Molecular modelling and time-resolved titration experiments of finned zeolites probe internal diffusion and reveal substantial improvements in mass transport, consistent with catalytic tests of a model reaction, which show that these structures behave as pseudo-nanocrystals with sizes commensurate to that of the fin. This approach could be extended to the rational synthesis of other zeolite and aluminosilicate materials.
RESUMEN
We present a set of experimental results showing a combination of various effects, that is, surface recombination velocity, surface charge traps, strain, and structural defects, that govern the carrier dynamics of self-catalyzed GaAs/AlGaAs core-shell nanowires (NWs) grown on a Si(111) substrate by molecular beam epitaxy. Time-resolved photoluminescence of NW ensemble and spatially resolved cathodoluminescence of single NWs reveal that emission intensity, decay time, and carrier diffusion length of the GaAs NW core strongly depend on the AlGaAs shell thickness but in a nonmonotonic fashion. Although 7 nm AlGaAs shell can efficiently suppress the surface recombination velocity of the GaAs NW core, the influence of the surface charge traps and the strain between the core and the shell that redshift the luminescence of the GaAs NW core remain observable in the whole range of the shell thickness. In addition, the band bending effect induced by the surface charge traps can alter the scattering of the excess carriers inside the GaAs NW core at the core/shell interface. If the AlGaAs shell thickness is larger than 50 nm, the luminescence efficiency of the GaAs NW cores deteriorates, ascribed to defect formation inside the AlGaAs shell evidenced by transmission electron microscopy.
RESUMEN
Zeolite crystal growth mechanisms are not fully elucidated owing to their complexity wherein the formation of a particular zeolite can occur by more than one crystallization pathway. Here, we have conducted time-resolved dissolution experiments of MFI-type zeolite crystals in ammonium fluoride medium where detailed structural analysis allowed us to extrapolate and elucidate the possible mechanism of nucleation and crystal growth. A combination of electron and scanning probe microscopy shows that dissolution initiates preferentially at lattice defects and progressively removes defect zones to reveal a mosaic structure of crystalline domains within each zeolite crystal. This mosaic architecture evolves during the growth process, reflecting the changing conditions of zeolite formation that can be retroactively assessed during zeolite crystal dissolution. Moreover, a more general implication of this study is the establishment that dissolution can be used successfully as an ex situ technique to uncover details about crystal growth features inaccessible by other methods.