A transformative route to nanoporous manganese oxides of controlled oxidation states with identical textural properties

Jae Hwa Lee, Young Jin Sa, Tae Kyung Kim, Hoi Ri Moon, Sang Hoon Joo

Research output: Contribution to journalArticlepeer-review

101 Scopus citations

Abstract

Nanoporous nanocrystalline metal oxides with tunable oxidation states are crucial for controlling their catalytic, electronic, and optical properties. However, previous approaches to modulate oxidation states in nanoporous metal oxides commonly lead to the breakdown of the nanoporous structure as well as involve concomitant changes in their morphology, pore size, surface area, and nanocrystalline size. Herein, we present a transformative route to nanoporous metal oxides with various oxidation states using manganese oxides as model systems. Thermal conversion of Mn-based metal-organic frameworks (Mn-MOFs) at controlled temperature and atmosphere yielded a series of nanoporous manganese oxides with continuously tuned oxidation states: MnO, Mn3O 4, Mn5O8, and Mn2O3. This transformation enabled the preparation of low-oxidation phase MnO and metastable intermediate phase Mn5O8 with nanoporous architectures, which were previously rarely accessible. Significantly, nanoporous MnO, Mn3O4, and Mn5O8 had a very similar morphology, surface area, and crystalline size. We investigated the electrocatalytic activity of nanoporous manganese oxides for oxygen reduction reaction (ORR) to identify the role of oxidation states, and observed oxidation state-dependent activity and kinetics for the ORR.

Original languageEnglish
Pages (from-to)10435-10443
Number of pages9
JournalJournal of Materials Chemistry A
Volume2
Issue number27
DOIs
StatePublished - 21 Jul 2014

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