Unusual Stabilization of Zinc Peroxide by Manganese Oxide: Mechanistic Understanding by Temperature-Dependent EPR Studies

Alexander I. Shames; Ovadia Lev; Alexey A. Mikhaylov; Alexander G. Medvedev; Jenny Gun; Petr V. Prikhodchenko

doi:10.1021/acs.jpcc.9b04523

Unusual Stabilization of Zinc Peroxide by Manganese Oxide: Mechanistic Understanding by Temperature-Dependent EPR Studies

Alexander I. Shames, Ovadia Lev, Alexey A. Mikhaylov, Alexander G. Medvedev, Jenny Gun, Petr V. Prikhodchenko

Ben-Gurion University of the Negev, The Hebrew University of Jerusalem

Research output: Contribution to journal › Article › peer-review

Abstract

Nanocrystalline zinc peroxide is passivated against further oxidation by the addition of minute, substoichiometric amounts of potassium permanganate, which also endows it with increased thermal stability. The oxidation state of manganese and the passivation mechanism are deciphered by a comparative electron paramagnetic resonance (EPR) study of the manganese-doped zinc peroxide nanoparticles and manganese oxide formed by reduction of permanganate by hydrogen peroxide as well as unmodified ZnO₂ nanoparticles. Temperature-dependent in situ EPR studies at elevated temperatures allowed us to trace simultaneously the temperature-dependent changes in abundance of superoxide radicals and the formation of Mn(IV) species and also to identify Mn(III) species at cryotemperatures. We conclude that the passivation is caused by Mn(III) complexes that act as antioxidants removing superoxide radicals, which are abundant in zinc peroxide and even more so in the manganese-doped zinc peroxide.

Original language	American English
Pages (from-to)	20884-20892
Number of pages	9
Journal	Journal of Physical chemistry c
Volume	123
Issue number	34
DOIs	https://doi.org/10.1021/acs.jpcc.9b04523
State	Published - 29 Aug 2019

All Science Journal Classification (ASJC) codes

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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10.1021/acs.jpcc.9b04523

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title = "Unusual Stabilization of Zinc Peroxide by Manganese Oxide: Mechanistic Understanding by Temperature-Dependent EPR Studies",

abstract = "Nanocrystalline zinc peroxide is passivated against further oxidation by the addition of minute, substoichiometric amounts of potassium permanganate, which also endows it with increased thermal stability. The oxidation state of manganese and the passivation mechanism are deciphered by a comparative electron paramagnetic resonance (EPR) study of the manganese-doped zinc peroxide nanoparticles and manganese oxide formed by reduction of permanganate by hydrogen peroxide as well as unmodified ZnO2 nanoparticles. Temperature-dependent in situ EPR studies at elevated temperatures allowed us to trace simultaneously the temperature-dependent changes in abundance of superoxide radicals and the formation of Mn(IV) species and also to identify Mn(III) species at cryotemperatures. We conclude that the passivation is caused by Mn(III) complexes that act as antioxidants removing superoxide radicals, which are abundant in zinc peroxide and even more so in the manganese-doped zinc peroxide.",

author = "Shames, \{Alexander I.\} and Ovadia Lev and Mikhaylov, \{Alexey A.\} and Medvedev, \{Alexander G.\} and Jenny Gun and Prikhodchenko, \{Petr V.\}",

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doi = "10.1021/acs.jpcc.9b04523",

language = "American English",

volume = "123",

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T1 - Unusual Stabilization of Zinc Peroxide by Manganese Oxide

T2 - Mechanistic Understanding by Temperature-Dependent EPR Studies

AU - Shames, Alexander I.

AU - Lev, Ovadia

AU - Mikhaylov, Alexey A.

AU - Medvedev, Alexander G.

AU - Gun, Jenny

AU - Prikhodchenko, Petr V.

PY - 2019/8/29

Y1 - 2019/8/29

N2 - Nanocrystalline zinc peroxide is passivated against further oxidation by the addition of minute, substoichiometric amounts of potassium permanganate, which also endows it with increased thermal stability. The oxidation state of manganese and the passivation mechanism are deciphered by a comparative electron paramagnetic resonance (EPR) study of the manganese-doped zinc peroxide nanoparticles and manganese oxide formed by reduction of permanganate by hydrogen peroxide as well as unmodified ZnO2 nanoparticles. Temperature-dependent in situ EPR studies at elevated temperatures allowed us to trace simultaneously the temperature-dependent changes in abundance of superoxide radicals and the formation of Mn(IV) species and also to identify Mn(III) species at cryotemperatures. We conclude that the passivation is caused by Mn(III) complexes that act as antioxidants removing superoxide radicals, which are abundant in zinc peroxide and even more so in the manganese-doped zinc peroxide.

AB - Nanocrystalline zinc peroxide is passivated against further oxidation by the addition of minute, substoichiometric amounts of potassium permanganate, which also endows it with increased thermal stability. The oxidation state of manganese and the passivation mechanism are deciphered by a comparative electron paramagnetic resonance (EPR) study of the manganese-doped zinc peroxide nanoparticles and manganese oxide formed by reduction of permanganate by hydrogen peroxide as well as unmodified ZnO2 nanoparticles. Temperature-dependent in situ EPR studies at elevated temperatures allowed us to trace simultaneously the temperature-dependent changes in abundance of superoxide radicals and the formation of Mn(IV) species and also to identify Mn(III) species at cryotemperatures. We conclude that the passivation is caused by Mn(III) complexes that act as antioxidants removing superoxide radicals, which are abundant in zinc peroxide and even more so in the manganese-doped zinc peroxide.

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U2 - 10.1021/acs.jpcc.9b04523

DO - 10.1021/acs.jpcc.9b04523

M3 - Article

SN - 1932-7447

VL - 123

SP - 20884

EP - 20892

JO - Journal of Physical chemistry c

JF - Journal of Physical chemistry c

IS - 34

ER -

Unusual Stabilization of Zinc Peroxide by Manganese Oxide: Mechanistic Understanding by Temperature-Dependent EPR Studies

Abstract

All Science Journal Classification (ASJC) codes

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