Spectroscopic capture of a low-spin Mn(IV)-oxo species in Ni-Mn3O4 nanoparticles during water oxidation catalysis.

High-valent metal-oxo moieties have been implicated as key intermediates preceding various oxidation processes. The critical O-O bond formation step in the Kok cycle that is presumed to generate molecular oxygen occurs through the high-valent Mn-oxo species of the water oxidation complex, i.e., the Mn4Ca cluster in photosystem II. Here, we report the spectroscopic characterization of new intermediates during the water oxidation reaction of manganese-based heterogeneous catalysts and assign them as low-spin Mn(IV)-oxo species. Recently, the effects of the spin state in transition metal catalysts on catalytic reactivity have been intensely studied; however, no detailed characterization of a low-spin Mn(IV)-oxo intermediate species currently exists. We demonstrate that a low-spin configuration of Mn(IV), S = 1/2, is stably present in a heterogeneous electrocatalyst of Ni-doped monodisperse 10-nm Mn3O4 nanoparticles via oxo-ligand field engineering. An unprecedented signal (g = 1.83) is found to evolve in the electron paramagnetic resonance spectrum during the stepwise transition from the Jahn-Teller-distorted Mn(III). In-situ Raman analysis directly provides the evidence for Mn(IV)-oxo species as the active intermediate species. Computational analysis confirmed that the substituted nickel species induces the formation of a z-axis-compressed octahedral C4v crystal field that stabilizes the low-spin Mn(IV)-oxo intermediates.