Time-Resolved Spectroscopy and High-Efficiency Light-Driven Hydrogen Evolution of a {Mo₃ S₄ }-Containing...

Polyoxothiometalate ions (ThioPOM) are active hydrogen-evolution reaction (HER) catalysts based on modular assembly built from electrophilic clusters {MoS_x } and vacant polyoxotungstates. Herein, the dumbbell-like anion [{(PW₁₁ O₃₉ )Mo₃ S₄ (H₂ O)₃ (OH)}₂ ]^8- exhibits very high light-driven HER activity, while the active cores {Mo₃ S₄ } do not contain any exposed disulfido ligands, which were suspected to be the origin of the HER activity. Moreover, in the catalyst architecture, the two central {Mo₃ S₄ } cores are sandwiched by two {PW₁₁ O₃₉ }^7- subunits that act as oxidant-resistant protecting groups and behave as electron-collecting units. A detailed photophysical study was carried out confirming the reductive quenching mechanism of the photosensitizer [Ir(ppy)₂ (dtbbpy)]⁺ by the sacrificial donor triethanolamine (TEOA) and highlighting the very high rate constant of the electron transfer from the reduced photosensitizer to the ThioPOM catalyst. Such results provide new insights into the field of molecular catalytic systems able to promote high HER activity.