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

Sunghak Park, Kyoungsuk Jin, Hyung Kyu Lim, Jin Kim, Kang Hee Cho, Seungwoo Choi, Hongmin Seo, Moo Young Lee, Yoon Ho Lee, Sangmoon Yoon, Miyoung Kim, Hyungjun Kim (), Sun Hee Kim () and Ki Tae Nam ()
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Sunghak Park: Seoul National University
Kyoungsuk Jin: Seoul National University
Hyung Kyu Lim: Division of Chemical Engineering and Bioengineering, Kangwon National University
Jin Kim: Western Seoul Center, Korea Basic Science Institute (KBSI)
Kang Hee Cho: Seoul National University
Seungwoo Choi: Seoul National University
Hongmin Seo: Seoul National University
Moo Young Lee: Seoul National University
Yoon Ho Lee: Seoul National University
Sangmoon Yoon: Seoul National University
Miyoung Kim: Seoul National University
Hyungjun Kim: Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST)
Sun Hee Kim: Western Seoul Center, Korea Basic Science Institute (KBSI)
Ki Tae Nam: Seoul National University

Nature Communications, 2020, vol. 11, issue 1, 1-10

Abstract: 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 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.

Date: 2020
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DOI: 10.1038/s41467-020-19133-w

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