Outstanding CO2 Photoreduction in Single‐Atom Thulium Modified Carbon Nitride

Abstract

AbstractCO2 reduction photocatalysts are favorable for obtaining renewable energy. Enriched active sites and effective photogenerated‐carriers separation are keys for improving CO2 photo‐reduction. A thulium (Tm) single atom tailoring strategy introducing carbon vacancies in porous tubular graphitic carbon nitride (g‐C3N4) surpassing the ever‐reported g‐C3N4 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 CO2 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 CO2 photo‐reduction. This work not only provides guidelines for CO2 photo‐reduction catalysts design but also offers mechanistic insights into single‐atom based photocatalysts for solar fuel production.