Highly Asymmetric Phthalocyanine as a Sensitizer of Graphitic Carbon Nitride for Extremely Efficient Photocatalytic H-2 Production under Near-Infrared Light

Highly asymmetric zinc phthalocyanine derivative (Zn-tri-PcNc) with intense near-IR light (650-800 nm) absorption is utilized as a sensitizer to extend the spectral response region of graphitic carbon nitride (g-C3N4) from similar to 450 nm to more than 800 nm. Ultraviolet-visible light (UV-vis) diffuse reflectance absorption spectra (DRS), photoluminescence (PL) spectra, time-resolved photoluminescence spectra (TRPS), and energy band structure analyses are adopted to investigate the photogenerated electron transfer process between Zn-tri-PcNc and g-C3N4 on both thermodynamics. and dynamics aspects. After optimizing the photocatalytic condition and adding chenodeoxycholic acid (CDCA) as coadsorbent, Zn-tri-PcNc sensitized g-C3N4 photocatalyst shows a H-2 production efficiency of 125.2 mu mol h(-1) under visible/near-IR-light (lambda >= 500 nm) irradiation, corresponding to a turnover number (TON) of 5008 h(-1) with an extremely high apparent quantum yield (AQY) of 1.85% at 700 nm monochromatic light irradiation. The present work should be the rarely fundamental investigation on the utilization of near-IR light of solar radiation for the photocatalytic H-2 production from water splitting over a dye-sensitized semiconductor.