Ultrasmall gold nanoclusters (Au NCs) have recently gained enormous popularity as a newly emerging light harvester, but many fundamental aspects of their photoelectrochemical behavior are still largely unknown. Unlike traditional photoactive nanoparticles, the NC's core structure, rather than its size, is a key factor that dictates the physical properties of NCs because of a strong quantum confinement effect. Despite this importance, no effort has been made to elucidate the effect of the core structure on the photoelectrochemistry of Au NC-sensitized TiO 2 (Au NC−TiO 2 ). Using Au 25 NC as a model system, we delicately tailored the icosahedral Au 13 core of Au 25 NC into a cuboctahedral Au 15 core of Au 23 NC. This subtle core manipulation has a drastic impact on the entire interfacial behavior of Au NC−TiO 2 , which in turn significantly affects the photoelectrochemical performance. This new insight highlights the overlooked effect of the core structure on the photoelectrochemistry of Au NC−TiO 2 .
Storefront retail is highly valued because of its contribution to street life, its pedestrian-oriented urban design quality, and its ability to foster social connection. Despite this valuation, in many areas, main street retail struggles and storefront vacancies are common. To better understand retail vacancy causes, effects, and mitigation, we conducted 18 in-depth (in-person or phone) interviews of the leaders of business organizations in Chicago. From the literature, common explanations for retail vacancy include structural transformation of the retail industry, demographic change, and the increased cost of being a retailer. Responses from our interviewees cited demographic change, urban context, and property owner behavior as the main reasons for retail vacancy. While there was significant overlap with the literature concerning the role of demographic change, our respondents put particular emphasis on contexts and behaviors witnessed at the “street level,” such as property owner behavior.
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