The striking influence of oxophilicity differences in heterometallic Mo-Mn oxide cluster reactions with water

摘要: Mixed-metal oxides have proven to be effective catalysts for the hydrogen evolution reaction, often outperforming either of binary metal oxides. The reactivity MnxMoOy− (x = 1, 2; y 3, 4) clusters toward H2O was investigated via time-of-flight mass spectrometry with clear evidence cluster oxidation and corresponding H2 production, specifically MnxMoO3− 2) clusters. Unlike previously studied MoxOy− clusters, which assumed a broad distribution stoichiometries (typically x ≤ 3x), both MnMoOy− Mn2MoOy− preferentially formed 3 4 compositions in significant quantities under our source conditions. electronic molecular structures MnxMoOy anion neutral were probed photoelectron spectroscopy analyzed supporting density functional theory calculations. Our studies suggest that centers are involved initial cluster–water complex formation, while Mo is center undergoes oxidation; hence, terminates when saturated its highest state +6. Across these four Mn remains relatively reduced stable high-spin configuration. preferential water molecules rather than rationalized by much lower relative oxophilicity Mn.Mixed-metal ...