Synthesis of Cu/CeO_2-x Nanocrystalline Heterodimers with Interfacial Active Sites To Promote CO₂ Electroreduction    

Synergistic effects at metal/metal oxide interfaces often give rise to highly active and selective catalytic motifs. So far, such interactions have been rarely explored to enhance the selectivity in the electrochemical CO₂ reduction reaction (CO₂RR). Herein, Cu/CeO_2-x heterodimers (HDs) are synthesized and presented as one of the prime examples where such effects promote CO₂RR. A colloidal seeded-growth synthesis is developed to connect the two highly mismatched domains (Cu and CeO_2-x) through an interface. The Cu/CeO_2-x HDs exhibit state-of-the-art selectivity toward CO₂RR (up to ∼80%) against the competitive hydrogen evolution reaction (HER) and high faradaic efficiency for methane (up to ∼54%) at −1.2 V_RHE, which is ∼5 times higher than that obtained when the Cu and CeO_2-x nanocrystals are physically mixed. Operando X-ray absorption spectroscopy along with other ex-situ spectroscopies evidences the partial reduction of Ce⁴⁺ to Ce³⁺ in the HDs during CO₂RR. A Density Functional Theory (DFT) study of the active site motif in reducing condition reveals synergistic effects in the electronic structure at the interface. The proposed lowest free energy pathway utilizes an O-vacancy site with intermediates binding to both Cu and Ce atoms, a configuration which allows one to break the CHO*/CO* scaling relation. The suppression of HER is attributed to the spontaneous formation of CO* at this interfacial motif and subsequent blockage of the Cu-sites.