Determining Structure Activity Relationships in Oxide Derived Cu Sn Catalysts During CO2 Electroreduction Using X Ray Spectroscopy

The development of earth abundant catalysts for selective electrochemical CO2 conversion is a central challenge. Cu amp; 63743;Sn bimetallic catalysts can yield selective CO2 reduction toward either CO or formate. This study presents oxide derived Cu amp; 63743;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 amp; 8776;70 at. consisting of both metallic Sn0 and Sn oxide species. Density functional theory simulations suggest that Sn amp; 948; 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 catalyst

Overlapping political budget cycles in the legislative and the executive

We advance the literature on political budget cycles by testing separately for cycles in expenditures for elections in the legislative and the executive. Using municipal data, we can separately identify these cycles and account for general year effects. For the executive branch, we show that it is important whether the incumbent re-runs. To account for the potential endogeneity associated with this decision, we apply a unique instrumental variables approach based on age and pension eligibility rules. We find sizable and significant effects in expenditures before council elections and before joint elections when the incumbent re-runs