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

^*Corresponding author for this work

Institute of Chemistry

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

8 Scopus citations

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

Bibliographical note

Funding Information:
The authors thank the Harvey M. Krueger Family Centre for Nanoscience and Nanotechnology. The research was supported by a Grant from the GIF, the German-Israeli Foundation for Scientific Research and Development. This research was partially supported by the Israel Science Foundation (grant No. 1215/19). The authors thank the Russian Science Foundation for financial support (grant 16-13-00110, ZnO 2 and ZnO 2 –MnO x nanoparticle synthesis and chemical characterization). The XRD measurements were performed using shared experimental facilities supported by IGIC RAS state assignment. The authors are grateful for Ivan Karpov’s help in the design of the cover art.

Publisher Copyright:
Copyright © 2019 American Chemical Society.

Access to Document

10.1021/acs.jpcc.9b04523

Cite this

@article{9158c6fbd0824a0da0e473580accaafb,

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.}",

note = "Funding Information: The authors thank the Harvey M. Krueger Family Centre for Nanoscience and Nanotechnology. The research was supported by a Grant from the GIF, the German-Israeli Foundation for Scientific Research and Development. This research was partially supported by the Israel Science Foundation (grant No. 1215/19). The authors thank the Russian Science Foundation for financial support (grant 16-13-00110, ZnO 2 and ZnO 2 –MnO x nanoparticle synthesis and chemical characterization). The XRD measurements were performed using shared experimental facilities supported by IGIC RAS state assignment. The authors are grateful for Ivan Karpov{\textquoteright}s help in the design of the cover art. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = aug,

day = "29",

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

language = "American English",

volume = "123",

pages = "20884--20892",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

publisher = "American Chemical Society",

number = "34",

}

TY - JOUR

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.

N1 - Funding Information: The authors thank the Harvey M. Krueger Family Centre for Nanoscience and Nanotechnology. The research was supported by a Grant from the GIF, the German-Israeli Foundation for Scientific Research and Development. This research was partially supported by the Israel Science Foundation (grant No. 1215/19). The authors thank the Russian Science Foundation for financial support (grant 16-13-00110, ZnO 2 and ZnO 2 –MnO x nanoparticle synthesis and chemical characterization). The XRD measurements were performed using shared experimental facilities supported by IGIC RAS state assignment. The authors are grateful for Ivan Karpov’s help in the design of the cover art. Publisher Copyright: Copyright © 2019 American Chemical Society.

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.

UR - http://www.scopus.com/inward/record.url?scp=85070903972&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.9b04523

DO - 10.1021/acs.jpcc.9b04523

M3 - Article

AN - SCOPUS:85070903972

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

Bibliographical note

Access to Document

Other files and links

Fingerprint

Cite this