Effects of Traps on Photo-induced Interfacial Charge Transfer of Ag-TiO₂: Photoelectrochemical, Electrochemical and Spectroscopic Characterizations

Abstract

In the field of metal-semiconductor composites based plasmon-mediated chemical reactions, a clear and in-depth understanding of charge transfer and recombination mechanisms is crucial for improving plasmonic photocatalytic efficiency. However, the plasmonic photocatalytic reactions at the solid-liquid interface of the electrochemical systems involve complex processes with multiple elementary steps, multiple time scales, and multiple controlling factors. Herein, the combination of photoelectrochemical and electrochemical as well as spectroscopic characterizations has been successfully used to study the effects of traps on the photo-induced interfacial charge transfer of silver-titanium dioxide (Ag-TiO₂). The results show that the increase of surface hydroxyl groups may be the key reason leading to the increase of traps after the Ag deposition on the surface of TiO₂. The increased traps of Ag-TiO₂, including deep and shallow traps, subsequently lead to the quenching of fluorescence and the reduction of photocurrent in the UV region. But the enhanced trap recombination may also prolong the lifetime of carriers. The modulation of traps is bound to affect the interfacial charge transfer, and thus, change the amount and lifetime of hot carriers, which can be exploited to manipulate the molecular reactions at the Ag surface. Our work highlights the importance of traps at metal-semiconductor electrodes that may help utilize the hot carriers in plasmonic mediated chemical reactions.

Keywords

Plasmonic / Silver-titanium dioxide / Trap state / Charge transfer / Photoelectrochemical Characterization

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