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

ABSTRACT: 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 c

SUBMITTER: Park S 

PROVIDER: S-EPMC7567882 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature