Outstanding CO2 Photoreduction in Single‐Atom Thulium Modified Carbon Nitride

Abstract CO 2 reduction photocatalysts are favorable for obtaining renewable energy. Enriched active sites and effective photogenerated‐carriers separation are keys for improving CO 2 photo‐reduction. A thulium (Tm) single atom tailoring strategy introducing carbon vacancies in porous tubular graphitic carbon nitride (g‐C 3 N 4 ) surpassing the ever‐reported g‐C 3 N 4 based photocatalysts, with 199.47 µmol g −1 h −1 CO yield, 96.8% CO selectivity, 0.84% apparent quantum efficiency and excellent photocatalytic stability, is implemented in this work. Results revealed that in‐plane Tm sites and interlayer‐bridged Tm‐N charge transfer channels significantly enhanced the aggregation/transfer of photogenerated electrons thus promoting CO 2 adsorption/activation and contributing to *COOH intermediates formation. Meanwhile, Tm atoms and carbon vacancies both benefit for rich active sites and enhanced photogenerated‐charge separation, thus optimizing reaction pathway and leading to excellent CO 2 photo‐reduction. This work not only provides guidelines for CO 2 photo‐reduction catalysts design but also offers mechanistic insights into single‐atom based photocatalysts for solar fuel production.