In the present study, we investigate the effects of the applied external potential on a dye-sensitized NiO photocathode by time-resolved photoluminescence and femtosecond transient absorption spectroscopy under operating conditions. Instead of the anticipated acceleration of photoinduced hole injection from dye into NiO at a more negative applied potential, we observe that both hole injection and charge recombination are slowed down. We cautiously assign this effect to a variation in OH- ion concentration in the inner Helmholtz plane of the electrochemical double layer with applied potential, warranting further investigation for the realization of efficient solar fuel devices.
Keywords: NiO; dye-sensitized photocathode; in situ spectroscopy; photodynamics; transient absorption.