Photoelectrochemical water oxidation improved by pyridine N-oxide as a mimic of tyrosine-Z in photosystem II

Artificial photosynthesis provides a way to store solar energy in chemical bonds with water oxidation as a major challenge for creating highly efficient and robust photoanodes that mimic photosystem II. We report here an easily available pyridine N-oxide (PNO) derivative as an efficient electron transfer relay between an organic light absorber and molecular water oxidation catalyst on a nanoparticle TiO2 photoanode. Spectroscopic and kinetic studies revealed that the PNO/PNO+ couple closely mimics the redox behavior of the tyrosine/tyrosyl radical pair in PSII in improving light-driven charge separation via multi-step electron transfer. The integrated photoanode exhibited a 1 sun current density of 3 mA cm(-2) in the presence of Na2SO3 and a highly stable photocurrent density of >0.5 mA cm(-2) at 0.4 V vs. NHE over a period of 1 h for water oxidation at pH 7. The performance shown here is superior to those of previously reported organic dye-based photoanodes in terms of photocurrent and stability.