Determining Structure-Activity Relationships in Oxide Derived CuSn Catalysts During CO2 Electroreduction Using X-Ray Spectroscopy

The development of earth-abundant catalysts for selective electrochemical CO2 conversion is a central challenge. Cu-Sn bimetallic catalysts can yield selective CO2 reduction toward either CO or formate. This study presents oxide-derived Cu-Sn catalysts tunable for either product and seeks to understand the synergetic effects between Cu and Sn causing these selectivity trends. The materials undergo significant transformations under CO2 reduction conditions, and their dynamic bulk and surface structures are revealed by correlating observations from multiple methods—X-ray absorption spectroscopy for in situ study, and quasi in situ X-ray photoelectron spectroscopy for surface sensitivity. For both types of catalysts, Cu transforms to metallic Cu0 under reaction conditions. However, the Sn speciation and content differ significantly between the catalyst types: the CO-selective catalysts exhibit a surface Sn content of 13 at. % predominantly present as oxidized Sn, while the formate-selective catalysts display an Sn content of ≈70 at. % consisting of both metallic Sn0 and Sn oxide species. Density functional theory simulations suggest that Snδ+ sites weaken CO adsorption, thereby enhancing CO selectivity, while Sn0 sites hinder H adsorption and promote formate production. This study reveals the complex dependence of catalyst structure, composition, and speciation with electrochemical bias in bimetallic Cu catalysts

Structure and fragmentation of growling grass frog metapopulations

Metapopulations occur in fragmented landscapes, and consist of demographically-independent populations connected by dispersal. Nevertheless, anthropogenic habitat fragmentation may be fatal to metapopulations, as it disrupts dispersal and gene flow, and undermines the balance between population extinction and colonization. Understanding the extent to which particular land-use practices disrupt dispersal and gene flow is therefore crucial for conserving metapopulations. We examined the structure and fragmentation of metapopulations of the endangered growling grass frog (Litoria raniformis) in an urbanizing landscape in southern Australia. Population clustering analyses revealed three distinct genetic units, corresponding to the three wetland clusters sampled. Isolation-by-distance was apparent between populations, and genetic distance was significantly correlated with the presence of urban barriers between populations. Our study provides evidence that urbanization fragments metapopulations of L. raniformis. Managers of L. raniformis in urbanizing landscapes should seek to mitigate effects of urbanization on dispersal and gene flow.Joshua M. Hale, Geoffrey W. Heard, Katie L. Smith, Kirsten M. Parris, Jeremy J. Austin, Michael Kearney, Jane Melvill