Fluorine‐Tuned of Ni Single‐Atom Catalysts for Efficient pH‐Universal CO ₂ Reduction via <i>d</i> ‐Orbital Modulation

ABSTRACT Electrocatalytic CO 2 reduction reaction (CO 2 RR) driven by renewable electricity is crucial for sustainable energy cycles and carbon neutrality. Developing cost‐effective and efficient electrocatalysts remains a key challenge. Herein, we report a fluorine‐regulated Ni single‐atom catalyst (NiFN‐900) prepared by self‐assembly of biomass and phthalocyanine molecules, and the subsequent controllable pyrolysis process, which exhibits remarkable CO 2 RR performance, achieving industrial‐level current density (> 200 mA cm −2 ) and Faradaic efficiency (> 90%) toward the CO 2 ‐to‐CO conversion under pH‐universal conditions. Detailed theoretical analysis revealed that the synergistic effects of pyrrolic N‐coordinated Ni sites and the semi‐ionic C‐F bonds simultaneously optimize the adsorption of *COOH intermediates by d ‐orbital modulation and suppress the hydrogen evolution reaction by altering surface affinity of *H species. This dual functionality enables exceptional pH‐universal CO 2 RR performance. Our low‐cost, biomass‐derived approach offers scalable electrocatalyst design for practical CO 2 utilizations.