Charge-Separated Pd^δ--Cu^δ+ Atom Pairs Promote CO₂ Reduction to C₂

Positively charged Cu sites have been confirmed to significantly promote the production of multicarbon (C₂) products from an electrochemical CO₂ reduction reaction (CO₂RR). However, the positively charged Cu has difficulty in existing under a strong negative bias. In this work, we design a Pd^δ--Cu₃N catalyst containing charge-separated Pd^δ--Cu^δ+ atom pair that can stabilize the Cu^δ+ sites. In situ characterizations and density functional theory reveal that the first reported negatively charged Pd^δ- sites exhibited a superior CO binding capacity together with the adjacent Cu^δ+ sites, synergistically promoting the CO dimerization process to produce C₂ products. As a result, we achieve a 14-fold increase in the C₂ product Faradaic efficiency (FE) on Pd^δ--Cu₃N, from 5.6% to 78.2%. This work provides a new strategy for synthesizing negative valence atom-pair catalysts and an atomic-level modulation approach of unstable Cu^δ+ sites in the CO₂RR.