Ethylene C-H Bond Activation by Neutral Mn2O5 Clusters under Visible Light Irradiation.

A photo excitation fast flow reactor coupled with a single-photon ionization (118 nm, 10.5 eV) time-of-flight mass spectrometry (TOFMS) instrument is used to investigate reactions of neutral MnmOn clusters with C2H4 under visible (532 nm) light irradiation. Association products Mn2O5(C2H4) and Mn3O6,7(C2H4) are observed without irradiation. Under light irradiation, the Mn2O5(C2H4) TOFMS feature decreases, and a new species, Mn2O5H2, is observed. This light-activated reaction suggests that the visible radiation can induce the chemistry, Mn2O5 + C2H4 + hv(532 nm) → Mn2O5*(C2H4) → Mn2O5H2 + C2H2. High barriers (0.67 and 0.59 eV) are obtained on the ground-state potential energy surface (PES); the reaction is barrierless and thermodynamically favorable on the first excited-state PES, as performed by time-dependent density functional theory calculations. The calculational and experimental results suggest that Mn2O5-like structures on manganese oxide surfaces are the appropriate active catalytic sites for visible light photocatalysis of ethylene dehydrogenation.