Photoelectrochemical Conversion from Graphitic C₃N₄ Quantum Dot Decorated Semiconductor Nanowires

Abstract

Despite the recent progress of developing graphitic carbon nitride (g-C3N4) as a metal-free photocatalyst, the synthesis of nanostructured g-C3N4 has still remained a complicated and time-consuming approach from its bulk powder, which substantially limits its photoelectrochemical (PEC) applications as well as the potential to form composites with other semiconductors. Different from the labor-intensive methods used before, such as exfoliation or assistant templates, herein, we developed a facile method to synthesize graphitic C3N4 quantum dots (g-CNQDs) directly grown on TiO2 nanowire arrays via a one-step quasi-chemical vapor deposition (CVD) process in a homemade system. The as-synthesized g-CNQDs uniformly covered over the surface of TiO2 nanowires and exhibited attractive photoluminescence (PL) properties. In addition, compared to pristine TiO2, the heterojunction of g-CNQD-decorated TiO2 nanowires showed a substantially enhanced PEC photocurrent density of 3.40 mA/cm(2) at 0 V of applied potential vs Ag/AgCl under simulated solar light (300 mW/cm(2)) and excellent stability with ∼82% of the photocurrent retained after over 10 h of continuous testing, attributed to the quantum and sensitization effects of g-CNQDs. Density functional theory calculations were further carried out to illustrate the synergistic effect of TiO2 and g-CNQD. Our method suggests that a variety of g-CNQD-based composites with other semiconductor nanowires can be synthesized for energy applications.