Because of inefficient charge utilization caused by localized π-electron conjugation and large exciton binding energy, the photoelectrochemical water-splitting efficiency of organic polymers is seriously limited. Taking the graphitic carbon nitride (g-CN) polymer as an example, we report a novel photoanode based on a vertically aligned g-CN porous nanorod (PNR) array prepared in situ, using a thermal polycondensation approach, with anodic aluminum oxide as the template. The g-CN PNR array exhibits an excellent photocurrent density of 120.5 μA cm-2 at 1.23 VRHE under one sun illumination, the highest reported incident photon-to-current efficiency of ∼15% at 360 nm, and an outstanding oxygen evolution reaction stability in 0.1 M Na2SO4 aqueous solution, which constitutes a benchmark performance among the reported g-CN-based polymer photoanodes without any sacrificial reagents. When compared with its planar counterpart, the enhanced performance of the PNR array results principally from its unique structure that enables a high degree of aromatic ring π-electron conjugation for higher mobility of charge carriers, provides a direct pathway for the electron transport to the substrate, produces a large portion of hole-accepting defect sites and space charge region to promote exciton dissociation, and also withstands more strain at the interface to ensure intimate contact with the substrate. This work opens a new avenue to develop nanostructured organic semiconductors for large-scale application of solar energy conversion devices.
Keywords: Charge separation; exciton dissociation; graphitic carbon nitride; photoanode; porous nanorod array; solar water splitting.