LAUSR

Gold nanoclusters (NCs) can be used as sensitizers to extend the absorption capabilities of TiO2 as photoelectrodes. However, the adsorption of NCs also creates additional surface states on the TiO2 surface, which gives rise to intricacies in the understanding of various interfacial phenomena occurring in NC-sensitized TiO2. One of the complexities that have recently been discovered is the size-dependent hole-transfer mechanism. In this work, we reveal another anomalous behavior in the hole-transfer process that the hole scavenging ability of the electrolyte also plays a role in determining the hole-transfer mechanism in the NC-TiO2 system, which is unprecedented in other photoelectrode systems. In the presence of an efficient hole scavenger (Na2SO3), the hole transfer in Au18-TiO2 occurs directly through the highest occupied molecular orbital (HOMO) of Au18 NCs. However, in the presence of a less efficient hole scavenger (ethylenediaminetetraacetic acid), hole transfer in Au18-TiO2 does not occur through the HOMO and shifts to surface state-assisted hole transfer. Due to surface state charging, this surface state-assisted hole-transfer mechanism results in delayed photocurrent response in Au18-TiO2. Evidence for this exotic hole-transfer mechanism shift is provided by photoelectrochemical electrochemical impedance spectroscopy, and its implications are discussed.