Synergistic Functionality of Dopants and Defects in Co-Phthalocyanine/B-CN Z-Scheme Photocatalysts for Promoting Photocatalytic CO2 Reduction Reactions

Abstract

The realization of solar-light-driven CO₂ reduction reactions (CO₂ RR) is essential for the commercial development of renewable energy modules and the reduction of global CO₂ emissions. Combining experimental measurements and theoretical calculations, to introduce boron dopants and nitrogen defects in graphitic carbon nitride (g-C₃ N₄ ), sodium borohydride is simply calcined with the mixture of g-C₃ N₄ (CN), followed by the introduction of ultrathin Co phthalocyanine through phosphate groups. By strengthening H-bonding interactions, the resultant CoPc/P-BNDCN nanocomposite showed excellent photocatalytic CO₂ reduction activity, releasing 197.76 and 130.32 µmol h^-1 g^-1 CO and CH₄ , respectively, and conveying an unprecedented 10-26-time improvement under visible-light irradiation. The substantial tuning is performed towards the conduction and valance band locations by B-dopants and N-defects to modulate the band structure for significantly accelerated CO₂ RR. Through the use of ultrathin metal phthalocyanine assemblies that have a lot of single-atom sites, this work demonstrates a sustainable approach for achieving effective photocatalytic CO₂ activation. More importantly, the excellent photoactivity is attributed to the fast charge separation via Z-scheme transfer mechanism formed by the universally facile strategy of dimension-matched ultrathin (≈4 nm) metal phthalocyanine-assisted nanocomposites.

Keywords: CO 2 reduction reactions; Z-scheme charge transfer mechanism; charge separation; cobalt phthalocyanine; nitrogen defects and boron dopants.