RESUMEN
Investigating how grain structure affects the functional properties of nanoparticles requires a robust method for nanoscale grain mapping. In this study, we directly compare the grain mapping ability of transmission Kikuchi diffraction (TKD) in a scanning electron microscope to automated crystal orientation mapping (ACOM) in a transmission electron microscope across multiple nanoparticle materials. Analysis of well-defined Au, ZnO, and ZnSe nanoparticles showed that the grain orientations and GB geometries obtained by TKD are accurate and match those obtained by ACOM. For more complex polycrystalline Cu nanostructures, TKD provided an interpretable grain map whereas ACOM, with or without precession electron diffraction, yielded speckled, uninterpretable maps with orientation errors. Acquisition times for TKD were generally shorter than those for ACOM. Our results validate the use of TKD for characterizing grain orientation and grain boundary distributions in nanoparticles, providing a framework for the broader exploration of how microstructure influences nanoparticle properties.
RESUMEN
The ability to functionalize hydrocarbons with CO2 could create opportunities for high-volume CO2 utilization. However, current methods to form carbon-carbon bonds between hydrocarbons and CO2 require stoichiometric consumption of very resource-intensive reagents to overcome the low reactivity of these substrates. Here, we report a simple semi-continuous cycle that converts aromatic hydrocarbons, CO2 and alcohol into aromatic esters without consumption of stoichiometric reagents. Our strategy centres on the use of solid bases composed of an alkali carbonate (M2CO3, where M+ = K+ or Cs+) dispersed over a mesoporous support. Nanoscale confinement disrupts the crystallinity of M2CO3 and engenders strong base reactivity at intermediate temperatures. The overall cycle involves two distinct steps: (1) CO32--promoted C-H carboxylation, in which the hydrocarbon substrate is deprotonated by the supported M2CO3 and reacts with CO2 to form a supported carboxylate (RCO2M); and (2) methylation, in which RCO2M reacts with methanol and CO2 to form an isolable methyl ester with concomitant regeneration of M2CO3.
RESUMEN
Defects such as dislocations and grain boundaries often control the properties of polycrystalline materials. In nanocrystalline materials, investigating this structure-function relationship while preserving the sample remains challenging because of the short length scales and buried interfaces involved. Here we use Bragg coherent diffractive imaging to investigate the role of structural inhomogeneity on the hydriding phase transformation dynamics of individual Pd grains in polycrystalline films in three-dimensional detail. In contrast to previous reports on single- and polycrystalline nanoparticles, we observe no evidence of a hydrogen-rich surface layer and consequently no size dependence in the hydriding phase transformation pressure over a 125-325 nm size range. We do observe interesting grain boundary dynamics, including reversible rotations of grain lattices while the material remains in the hydrogen-poor phase. The mobility of the grain boundaries, combined with the lack of a hydrogen-rich surface layer, suggests that the grain boundaries are acting as fast diffusion sites for the hydrogen atoms. Such hydrogen-enhanced plasticity in the hydrogen-poor phase provides insight into the switch from the size-dependent behavior of single-crystal nanoparticles to the lower transformation pressures of polycrystalline materials and may play a role in hydrogen embrittlement.
RESUMEN
Polycrystalline material properties depend on the distribution and interactions of their crystalline grains. In particular, grain boundaries and defects are crucial in determining their response to external stimuli. A long-standing challenge is thus to observe individual grains, defects, and strain dynamics inside functional materials. Here we report a technique capable of revealing grain heterogeneity, including strain fields and individual dislocations, that can be used under operando conditions in reactive environments: grain Bragg coherent diffractive imaging (gBCDI). Using a polycrystalline gold thin film subjected to heating, we show how gBCDI resolves grain boundary and dislocation dynamics in individual grains in three-dimensional detail with 10-nanometer spatial and subangstrom displacement field resolution. These results pave the way for understanding polycrystalline material response under external stimuli and, ideally, engineering particular functions.
