4.6 Article

Ozone Decomposition Mechanism at Different Structural Oxygen Vacancies on Manganese Dioxide

Journal

JOURNAL OF PHYSICAL CHEMISTRY C
Volume 126, Issue 40, Pages 17076-17083

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.2c05265

Keywords

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Funding

  1. National Key R&D Program of China
  2. Natural Science Foundation of Shanghai
  3. Shanghai Institute of Pollution Control and Ecological Security
  4. [2019YFC1904001]
  5. [21ZR1468000]

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The study found that MnO2 has two different oxygen vacancies, and the catalytic decomposition efficiency of [Mn3+]-V0-[Mn3+] is significantly higher than that of [Mn3+]-V0. MnO2 with [Mn3+]-V0-[Mn3+] has a lower average oxidation state of Mn and faster electron transfer capacity. A new mechanism of ozone decomposition on [Mn3+]-V0-[Mn3+] was proposed.
MnO2 is a promising catalyst for ozone decom-position, and oxygen vacancy has been regarded as the determinant factor for decomposition effectiveness. MnO2 with two different oxygen vacancies, that is, [Mn3+]-V0-[Mn3+] and [Mn3+]-V0, was synthesized and characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spec-troscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The catalytic decomposition rate of [Mn3+]-V0- [Mn3+] was significantly greater than that of [Mn3+]-V0. MnO2 with [Mn3+]-V0-[Mn3+] showed the lowest average oxidation state of Mn and the fastest electron transfer capacity. A new pathway for ozone decomposition at [Mn3+]-V0-[Mn3+] was proposed accordingly. The reaction sequence involved (i) dissociative adsorption of ozone to form an oxygen molecule and an atomic O- at [Mn3+], (ii) reaction of O- further with another O3 molecule to form [Mn4+]-O-O-[Mn4+], and (iii) [Mn4+]-O-O-[Mn4+] decomposition to form a gas-phase oxygen molecule and [Mn3+]-V0-[Mn3+] for further ozone adsorption. This work revealed a new avenue for designing efficient catalysts for ozone elimination.

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