(469e) Designing Cu-Based Bimetallic Nanoparticles for CO2 Activation

Copper-based catalysts are good candidates for the conversion of carbon dioxide into useful chemicals. Using Density Functional Theory calculations, we investigate the adsorption and activation of carbon dioxide on CuM (M = Au, Cu, Mn, Mo, Ni, Pd, Rh, Ru, Sc, V, Zn, and Zr) nanoparticles. Candidate heteroatoms (M) for CO₂ adsorption were selected based on the heteroatom preference to occupy a surface site of the nanoparticle. We identified two significant descriptors for carbon dioxide chemisorption on the nanoparticles: (1) the heteroatom local d-band center must be positioned higher in energy than the LUMO of carbon dioxide, and (2) the electropositivity of the heteroatom must be higher compared to Cu. Both descriptors lead to an effective charge transfer from the nanoparticle to CO₂. Using these criteria, bimetallic nanoparticles can be screened rapidly for the ability to chemisorb (and activate) CO₂, which is an important step for the subsequent catalytic conversion of CO₂. Our work highlights the importance of generating binding sites on a nanoparticle surface based on stability and electronic structure properties, which can lead to designing bifunctional catalysts.