Noble Metal Free, Visible Light Driven Photocatalysis Using TiO₂ Nanotube Arrays Sensitized by P‐Doped C₃N₄ Quantum Dots

Abstract Bulk g‐C₃N₄ is an earth‐abundant, easily synthesizable, and exceptionally stable photocatalyst with an electronic bandgap of 2.7 eV. Herein, the concepts of P‐doping and size quantization are combined to synthesize highly fluorescent P‐doped carbon nitride quantum dots (CNPQDs) with a bandgap of 2.1 eV. CNPQDs are hosted on anatase‐phase and rutile‐phase TiO₂ nanotube array scaffolds, and examined as photoanodes for sunlight‐driven water‐splitting and as photocatalysts for surface catalytic reactions. Square‐shaped rutile phase TiO₂ nanotube arrays (STNAs) decorated with CNPQDs (CNPQD‐STNA) generate 2.54 mA cm⁻² photocurrent under AM1.5 G simulated sunlight. A champion hydrogen evolution rate of 22 µmol h⁻¹ corresponds to a Faradaic efficiency of 93.2%. In conjunction with Ag nanoparticles (NPs), the CNPQD‐STNA hybrid is also found to be an excellent plexcitonic photocatalyst for the visible light‐driven transformation of 4‐nitrobenzenethiol (4‐NBT) to dimercaptoazobenzene (DMAB), producing reaction completion at a laser power of 1 mW (532 nm) while Ag NP/TNA and Ag NP/STNA photocatalysts cannot complete this transformation even at 10 mW laser power. The results point the way forward for photochemically robust, noble metal free, visible light harvesting photoacatalysts based on nanostructured heterojunctions of graphenic frameworks with TiO₂.