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Nano Research 2023, 16(5): 6316-6325 https://doi.org/10.1007/s12274-023-5624-z
Research Article | Issue | Published: 25 March 2023

Electron transfer to direct oxidation of aqueous organics by perovskites

Show Author's Information Tao Kong1,  Yuxian Wang1( ),  Shenning Liu1,  Ya Liu1,2,  Menghan Zhou1,  Bofeng Li1,  Xiaoguang Duan2,  Chunmao Chen1( ),  Shaobin Wang2( )
State Key Laboratory of Heavy Oil Processing, State Key Laboratory of Petroleum Pollution Control, China University of Petroleum (Beijing), Beijing 102249, China
School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA 5005, Australia
Keywords:
Ca-Mn-O perovskites, surface direct oxidation, electron transfer process, spin state regulation
Topics:
Catalytic oxidation
Cite this article:
Kong T, Wang Y, Liu S, et al. Electron transfer to direct oxidation of aqueous organics by perovskites. Nano Research, 2023, 16(5): 6316-6325. https://doi.org/10.1007/s12274-023-5624-z
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Abstract Full text Electronic supplementary material About this article

The residual of oxidant chemicals in advanced oxidation processes (AOPs) resulted in both economic cost and secondary pollution. Herein, we report a direct oxidation of phenolic pollutants induced by Ca-Mn-O perovskites without using an oxidant. Governed by one-electron transfer process (ETP) from the phenolics to the Ca-Mn-O perovskites, this direct oxidation proceeds in fast reaction kinetics with activation energy of 51.4 kJ/mol, which was comparable with those AOPs-based catalytic systems. Additionally, mineralization and polymerization reactions occurred on the Ca-Mn-O surface and ensured the complete removal of phenolics. The high spin state Mn(III) within Ca-Mn-O structure was the dominant active site for this ETP. The elongated axial Mn(III)–O bonds within the [MnO6] octahedron facilitated the acceptance of the electrons from the phenolics and thus promoted the initiation of the direct oxidation process. Mn(III) in the high spin state can also activate dissolved O2 to produce singlet oxygen (1O2) for a fast removal of phenolics. The mixed Mn(III)/Mn(IV) within Ca-Mn-O accelerated the ETP by enhancing the electrical conductivity. This efficient Ca-Mn-O-induced ETP for removal of organic contaminants casts off the dependence on external chemical and energy inputs and provides a sustainable approach for transforming the toxic organic pollutants into value-added polymers.


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Electronic supplementary material
About this article

Electron transfer to direct oxidation of aqueous organics by perovskites

Show Author's information Tao Kong1, Yuxian Wang1( ), Shenning Liu1, Ya Liu1,2, Menghan Zhou1, Bofeng Li1, Xiaoguang Duan2, Chunmao Chen1( ), Shaobin Wang2( )
State Key Laboratory of Heavy Oil Processing, State Key Laboratory of Petroleum Pollution Control, China University of Petroleum (Beijing), Beijing 102249, China
School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA 5005, Australia

Abstract

The residual of oxidant chemicals in advanced oxidation processes (AOPs) resulted in both economic cost and secondary pollution. Herein, we report a direct oxidation of phenolic pollutants induced by Ca-Mn-O perovskites without using an oxidant. Governed by one-electron transfer process (ETP) from the phenolics to the Ca-Mn-O perovskites, this direct oxidation proceeds in fast reaction kinetics with activation energy of 51.4 kJ/mol, which was comparable with those AOPs-based catalytic systems. Additionally, mineralization and polymerization reactions occurred on the Ca-Mn-O surface and ensured the complete removal of phenolics. The high spin state Mn(III) within Ca-Mn-O structure was the dominant active site for this ETP. The elongated axial Mn(III)–O bonds within the [MnO6] octahedron facilitated the acceptance of the electrons from the phenolics and thus promoted the initiation of the direct oxidation process. Mn(III) in the high spin state can also activate dissolved O2 to produce singlet oxygen (1O2) for a fast removal of phenolics. The mixed Mn(III)/Mn(IV) within Ca-Mn-O accelerated the ETP by enhancing the electrical conductivity. This efficient Ca-Mn-O-induced ETP for removal of organic contaminants casts off the dependence on external chemical and energy inputs and provides a sustainable approach for transforming the toxic organic pollutants into value-added polymers.

Keywords: Ca-Mn-O perovskites, surface direct oxidation, electron transfer process, spin state regulation

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Publication history
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Acknowledgements

Publication history

Received: 25 September 2022
Revised: 17 November 2022
Accepted: 27 February 2023
Published: 25 March 2023
Issue date: May 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgement

The authors greatly appreciate the financial supports from the National Natural Science Foundation of China (Nos. 21978324 and 22278436) and the Science Foundation of China University of Petroleum, Beijing (No. 2462021QNXZ009).

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