In situ and operando electron microscopy in heterogeneous catalysis - insights into multi-scale chemical dynamics

This review features state-of-the-art in situ and operando electron microscopy (EM) studies of heterogeneous catalysts in gas and liquid environments during reaction. Heterogeneous catalysts are important materials for the efficient production of chemicals/fuels on an industrial scale and for energy conversion applications. They also play a central role in various emerging technologies that are needed to ensure a sustainable future for our society. Currently, the rational design of catalysts has largely been hampered by our lack of insight into the working structures that exist during reaction and their associated properties. However, elucidating the working state of catalysts is not trivial, because catalysts are metastable functional materials that adapt dynamically to a specific reaction condition. The structural or morphological alterations induced by chemical reactions can also vary locally. A complete description of their morphologies requires that the microscopic studies undertaken span several length scales. EMs, especially transmission electron microscopes, are powerful tools for studying the structure of catalysts at the nanoscale because of their high spatial resolution, relatively high temporal resolution, and complementary capabilities for chemical analysis. Furthermore, recent advances have enabled the direct observation of catalysts under realistic environmental conditions using specialized reaction cells. Here, we will critically discuss the importance of spatially-resolved operando measurements and the available experimental setups that enable (1) correlated studies where EM observations are complemented by separate measurements of reaction kinetics or spectroscopic analysis of chemical species during reaction or (2) real-time studies where the dynamics of catalysts are followed with EM and the catalytic performance is extracted directly from the reaction cell that is within the EM column or chamber. Examples of current research in this field will be presented. Challenges in the experimental application of these techniques and our perspectives on the field's future directions will also be discussed

Comparative analysis of rigidity across protein families

We present a comparative study in which 'pebble game' rigidity analysis is applied to multiple protein crystal structures, for each of six different protein families. We find that the main-chain rigidity of a protein structure at a given hydrogen bond energy cutoff is quite sensitive to small structural variations, and conclude that the hydrogen bond constraints in rigidity analysis should be chosen so as to form and test specific hypotheses about the rigidity of a particular protein. Our comparative approach highlights two different characteristic patterns ('sudden' or 'gradual') for protein rigidity loss as constraints are removed, in line with recent results on the rigidity transitions of glassy networks

The Role of Solar Wind Hydrogen in Space Weathering: Insights from Laboratory-Irradiated Northwest Africa 12008

Micrometeoroid impacts, solar wind plasma interactions, and regolith gardening drive the complicated and nuanced mechanism of space weathering (or optical maturation); a process by which a materials optical properties are changed as a result of chemical and physical alterations at the surface of grains on airless bodies. Reddened slopes, attenuated absorption bands, and an overall reduction in albedo in the visible and near-IR wavelength ranges are primarily the result of native iron nanoparticle (npFe0) production within glassy rims that form from sputtering and vaporization. The sizes and abundance of these particles provide information about the relative surface exposure age of a particular grain. In addition, many studies have indicated that composition greatly affects the rate at which optical maturation occurs. Despite our understanding of how npFe0 affects optical signatures, the relative roles of micrometeoroid bombardment and solar wind interactions remains undetermined. To simulate the early effects of weathering by the solar wind and to determine thresholds for optical change with respect to a given mineral phase, we irradiated a fine-grained lunar basalt with 1 keV H+ to a fluence of 6.4 x 1016 H+ per sq.cm. Surface alterations within four phases have been evaluated using transmission electron microscopy (TEM). We found that for a given fluence of H+, the extent of damage acquired by each grain was dependent on its composition. No npFe(0) was produced in any of the phases evaluated in this study. These results are consistent with many previous studies conducted using ions of similar energy, but they also provide valuable information about the onset of space weathering and the role of the solar wind during the early stages of optical maturation