Research area | Chemistry and Materials Science and Technology |
Title | Active and Selective Ensembles in Oxide-Derived Copper Catalysts for CO2 Reduction |
Publication Type | Journal Article |
Publication year | 2020 |
Authors | Dattila, F, Garcia-Muelas, R, Lopez, N |
Journal | ACS ENERGY LETTERS |
Volume | 5 |
Number | 10 |
Pages | 3176-3184 |
Type of Article | Article |
Abstract | Copper catalysts are unique in CO2 reduction as they allow the formation of C2+ products. Depending on the catalysts' synthesis, product distribution varies significantly: while Cu nanoparticles produce mainly methane and hydrogen, oxide-derived copper leads to ethylene and ethanol. Here, by means of ab initio molecular dynamics on oxygen-depleted models, we identified the ensembles controlling catalytic performance. Upon reconstruction and irrespective of the starting structure, recurrent patterns defined by their coordination and charges appear: metallic Cu-0, polarized Cu delta+, and oxidic Cu+. These species combine to form 14 ensembles. Among them, 4-(6-)coordinated Cu adatoms and Cu3 delta+O3 are responsible for tethering CO2, while metastable near-surface oxygens in fcc-(111) or (100)-like Cu domains promote C-C bond formation via glyoxylate species, thus triggering selective C2+ production at low onset potentials. Our work provides guidelines for modeling complex structural rearrangements under CO2 reduction conditions and devising new synthetic protocols toward an enhanced catalytic performance. |
DOI | 10.1021/acsenergylett.0c01777 |