Time-Resolved IR Spectroscopy Reveals a Mechanism with TiO₂ as a Reversible Electron Acceptor in a TiO₂–Re Catalyst System for CO₂ Photoreduction

Attaching the phosphonated molecular catalyst [Re^IBr­(bpy)­(CO)₃]⁰ to the wide-bandgap semiconductor TiO₂ strongly enhances the rate of visible-light-driven reduction of CO₂ to CO in dimethylformamide with triethanolamine (TEOA) as sacrificial electron donor. Herein, we show by transient mid-IR spectroscopy that the mechanism of catalyst photoreduction is initiated by ultrafast electron injection into TiO₂, followed by rapid (ps-ns) and sequential two-electron oxidation of TEOA that is coordinated to the Re center. The injected electrons can be stored in the conduction band of TiO₂ on an ms-s time scale, and we propose that they lead to further reduction of the Re catalyst and completion of the catalytic cycle. Thus, the excited Re catalyst gives away one electron and would eventually get three electrons back. The function of an electron reservoir would represent a role for TiO₂ in photocatalytic CO₂ reduction that has previously not been considered. We propose that the increase in photocatalytic activity upon heterogenization of the catalyst to TiO₂ is due to the slow charge recombination and the high oxidative power of the Re^II species after electron injection as compared to the excited MLCT state of the unbound Re catalyst or when immobilized on ZrO₂, which results in a more efficient reaction with TEOA