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Iridium Nanocrystals Enriched with Defects and Atomic Steps to Enhance Oxygen Evolution Reaction Performance

The presence of defects can significantly improve catalytic activity and stability, as they influence the binding of the reactants, intermediates, and products to the catalyst. Controlling defects in the structures of nanocrystal catalysts is synthetically challenging. In this study, we demonstrate the ability to control the growth of Ir nanocrystals, enabling the tuning of both structural and surface defects. The Ir nanocrystals have unique structures that range from single crystals of a few nanometers to twinned nanoparticles and multiply twinned crystallites with a high density of atomic steps. Further, this approach of defect engineering enables us to understand their roles in enhancing the performance of the OER and producing an Ir catalyst with both high activity and stability. Our results show the importance of the concept of using synthetic control of structural and surface defects in metal nanoparticles as a strategy to improve catalytic performance.

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Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Fivefold and icosahedral symmetries induced by multiply twinned crystal structures have been studied extensively for their role in influencing the shape of synthetic nanoparticles, and solution chemistry or geometric confinement are widely considered to be essential. Here we report the purely entropy-driven formation of fivefold and icosahedral twinned clusters of particles in molecular simulation without geometric confinement or chemistry. Hard truncated tetrahedra self-assemble into cubic or hexagonal diamond colloidal crystals depending on the amount of edge and vertex truncation. By engineering particle shape to achieve a negligible entropy difference between the two diamond phases, we show that the formation of the multiply twinned clusters is easily induced. The twinned clusters are entropically stabilized within a dense fluid by a strong fluid-crystal interfacial tension arising from strong entropic bonding. Our findings provide a strategy for engineering twinning behavior in colloidal systems with and without explicit bonding elements between particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modified Winterbottom Construction Including Boundaries

There has been extensive work on the equilibrium shape of isolated nanoparticles with internal boundaries, and also single crystals on substrates. Surprisingly, almost shockingly, there has been very little work on the equilibrium shape of particles with internal boundaries on substrates. Here in this paper, the general solution is given for the configuration of particles which contain twin and other grain boundaries on a flat substrate, which can be applied to any polycrystalline or multiphase nanoparticle configuration. The solution is based upon combining the established modified-Wulff construction that has been extensively validated for twinned particles with the Winterbottom construction for single particles on a substrate. The solution is illustrated for the specific case of five-fold multiply twinned particles. Good agreement is observed between both existing experimental data in the literature as well as some experimental data included within this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗