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Stabilizing high dispersions of catalytically active metals is integral to improving the lifetime, activity, and material utilization of catalysts that are periodically exposed to high temperatures during operation or maintenance. We have found that annealing palladium-based core@shell catalysts in air at elevated temperatures (800 °C) promotes the redispersion of active metals into highly dispersed sites, which we refer to as halo sites. Here, we examine the restructuring of Pd@SiO2 and Pd@CeO2 core@shell catalysts over successive 800 °C aging cycles to understand the formation, activity, nanoscale structure, and stability of these palladium halo sites. While encapsulation generally improves metal utilization by providing a physical barrier that promotes redispersion over agglomeration, our cycled aging experiments demonstrate that halo sites are not stable in all catalysts. Halo sites continue to migrate in Pd@SiO2 due to poor metal–support bonding, which leads to palladium agglomeration. In contrast, halo sites formed in Pd@CeO2 remain stable. The dispersed palladium also synergistically stabilizes the ceria from agglomerating. We attribute this stability, in addition to an observed improvement in catalytic activity, to the coordination between palladium and reducible ceria that arises during the formation of halo sites. We probe the importance of ceria oxidation state on the stability of halo sites by aging Pd@CeO2 after it has been reduced. While some halo sites agglomerate, we find that returning to air aging mitigates the loss of these sites and catalytic activity. Our findings illustrate how nanoscale catalyst structures can be designed to promote the formation of highly stable and dispersed metal sites. [ABSTRACT FROM AUTHOR]

Rooftop solar thermal collectors have the potential to meet residential heating demands if deployed efficiently at low solar irradiance (i.e., 1 sun). The efficiency of solar thermal collectors depends on their ability to absorb incoming solar energy and minimize thermal losses. Most techniques utilize a vacuum gap between the solar absorber and the surroundings to eliminate conduction and convection losses, in combination with surface coatings to minimize reradiation losses. Here, we present an alternative approach that operates at atmospheric pressure with simple, black, absorbing surfaces. Silica based aerogels coated on black surfaces have the potential to act as simple and inexpensive solar thermal collectors because of their high transmission to solar radiation and low transmission to thermal radiation. To demonstrate their heat-trapping properties, we fabricated tetramethyl orthosilicate-based silica aerogels. A hydrophilic aerogel with a thickness of 1 cm exhibited a solar-averaged transmission of 76% and thermally averaged transmission of ≈1% (at 100 °C). To minimize unwanted solar absorption by O-H groups, we functionalized the aerogel to be hydrophobic, resulting in a solar-averaged transmission of 88%. To provide a deeper understanding of the link between aerogel properties and overall efficiency, we developed a coupled radiative-conductive heat transfer model and used it to predict solar thermal performance. Instantaneous solar thermal efficiencies approaching 55% at 1 sun and 80 °C were predicted. This study sheds light on the applicability of silica aerogels on black coatings for solar thermal collectors and offers design priorities for next-generation solar thermal aerogels.