Electrochemical CO₂ conversion offers a sustainable approach to alleviate the energy crisis but remains a long-standing challenge. Herein, atomically dispersed FeN₅ sites anchored on N-doped carbon matrix templated by zeolitic imidazole framework-8 (ZIF-8) are facilely synthesized for efficient catalyzing CO₂ reduction. The FeN₅ single-atom catalyst (Fe-SA/ZIF) presents the Faradaic efficiency of 98% at −0.7 V vs. RHE and over 95% in a wide potential range from −0.4 to −1.0 V vs. RHE, surpassing most of the reported single-atom catalysts for CO₂RR. Further density functional theory (DFT) calculations reveal that the outstanding activity of FeN₅ sites mainly originates from the lowered d-band center modulated by the out-of-plane coordinated pyridinic N, which reduces the CO adsorption energy from −1.71 to −1.49 eV compared to FeN₄ moieties. Thus, the synergistic effect between FeN₄ sites and the coordinated pyridine offers new insight in designing outstanding electrocatalysts for multiple applications.

电化学CO ₂转化为缓解能源危机提供了一种可持续的方法，但仍然是一项长期挑战。在此，容易地合成锚固在以沸石咪唑骨架8（ZIF-8）为模板的N掺杂碳基质上的原子分散的FeN ₅位点，以有效地催化CO ₂还原。汾₅单原子催化剂（FE-SA / ZIF）呈现98％的在-0.7V的法拉第效率VS。在-0.4至-1.0 V vs.的宽电位范围内，RHE和95％以上。RHE超过了大多数报道的CO ₂ RR单原子催化剂。进一步的密度泛函理论（DFT）计算表明，FeN ₅的出色活性这些位点主要来自平面外配位吡啶吡啶N调制的d波段中心降低，与FeN ₄部分相比，其将CO吸附能从-1.71降低到-1.49 eV 。因此，FeN ₄位点与配位吡啶之间的协同作用为设计适用于多种应用的出色电催化剂提供了新的见识。