Dynamically Stable Cu <sup>0</sup> Cu <sup>δ+</sup> Pair Sites Based on In Situ‐Exsolved Cu Nanoclusters on CaCO <sub>3</sub> for Efficient CO <sub>2</sub> Electroreduction
Rongrong Zhang, Haibin Ma, Shuhe Han, Zhitan Wu, Xin Zhou, Zhongxin Chen, Jia Liu, Yukun Xiao, Wei Chen, Kian Ping Loh
Abstract
Abstract Copper‐based catalysts are the choice for producing multi‐carbon products (C 2+ ) during CO 2 electroreduction (CO 2 RR), where the Cu 0 Cu δ+ pair sites are proposed to be synergistic hotspots for C−C coupling. Maintaining their dynamic stability requires precise control over electron affinity and anion vacancy formation energy, posing significant challenges. Here, we present an in situ reconstruction strategy to create dynamically stable Cu 0 Cu 0.18+ OCa motifs at the interface of exsolved Cu nanoclusters and CaCO 3 nanospheres (Cu/CaCO 3 ). In situ XAFS analysis confirmed the low‐valency state of Cu δ+ during CO 2 RR. DFT calculations demonstrated that the nanocluster size arises from the balance between metal‐support interactions and Cu−Cu cohesive energy, while the dynamic stability of rich interfacial Cu δ+ sites is attributed to their low electron affinity and high CO 3 2− vacancy formation energy, which collectively contribute to reduced reducibility. The transformed Cu/CaCO 3 exhibits an impressive C 2+ Faradaic efficiency of 83.7 % at a partial current density of 393 mA cm −2 , facilitated by adsorption of *CO with varying electronegativity at heterogeneous copper sites that lowers the C−C coupling energy barrier. Our findings establish insoluble carbonate as an effective anion pairing for Cu 0 Cu δ+ sites, highlighting the effectiveness of the in situ reconstitution strategy in producing a high density of dynamically stable Cu 0 Cu δ+ pair sites.