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Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2018, Vol. 12 Issue (4) : 790-797
Multivalent manganese oxides with high electrocatalytic activity for oxygen reduction reaction
Xiangfeng Peng1, Zhenhai Wang1, Zhao Wang1(), Yunxiang Pan2
1. School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin 300350, China
2. School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009, China
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A noble-metal-free catalyst based on both Mn3O4 and MnO was prepared by using the dielectric barrier discharge technique at moderate temperature. The prepared catalyst shows a higher electrocatalytic activity towards the oxygen reduction reaction than the catalyst prepared by using the traditional calcination process. The enhanced activity could be due to the coexistence of manganese ions with different valences, the higher oxygen adsorption capacity, and the suppressed aggregation of the catalyst nanoparticles at moderate temperature. The present work would open a new way to prepare low-cost and noble-metal-free catalysts at moderate temperature for more efficient electrocatalysis.

Keywords oxygen reduction reaction      manganese oxides      mixed valences of manganese      oxygen adsorption      dielectric barrier discharge     
Corresponding Author(s): Zhao Wang   
Just Accepted Date: 15 January 2018   Online First Date: 09 May 2018    Issue Date: 03 January 2019
 Cite this article:   
Xiangfeng Peng,Zhenhai Wang,Zhao Wang, et al. Multivalent manganese oxides with high electrocatalytic activity for oxygen reduction reaction[J]. Front. Chem. Sci. Eng., 2018, 12(4): 790-797.
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Xiangfeng Peng
Zhenhai Wang
Zhao Wang
Yunxiang Pan
Fig.1  Images of (a) KMnO4, (b) MnOx-D, and (c) MnOx-C samples; (d) XRD patterns of MnOx@C-C, MnOx@C-D, and MnOx@C-CD
Fig.2  TEM images of (a, b) MnOx@C-C and (c, d) MnOx@C-D
Fig.3  XPS spectra of (a) O1s spectra and (b) Mn2p spectra for MnOx@C-D, MnOx@C-CD and MnOx@C-C samples. The scatters stand for experiment data and the lines stand for fitting data
Sample Olatt Oads Owat
BE/eV Peak area/% BE /eV Peak area/% BE/eV Peak area/%
MnOx@C-CD 529.2 18.77 531.8 55.11 533.4 26.12
MnOx@C-D 529.0 8.65 531.8 60.00 533.2 31.35
MnOx@C-C 529.2 16.40 531.5 45.09 533.0 38.51
Tab.1  Summaries of binding energy (BE) and peak area percentages of different oxygen species for MnOx@C-CD, MnOx@C-D, and MnOx@C-C
Sample Mn(II) Mn(III) Mn(IV)
BE/eV Peak area/% BE/eV Peak area/% BE/eV Peak area/%
MnOx@C-CD 640.4 52.75 641.8 43.28 644.0 3.97
MnOx@C-D 640.1 61.95 641.6 12.37 642.3 25.68
MnOx@C-C 640.4 37.49 641.9 58.18 644.1 4.32
Tab.2  Summaries of BE and peak area percentages of different manganese species for MnOx@C-CD, MnOx@C-D, and MnOx@C-C
Fig.4  TPD-O2 profiles and integral areas of MnOx@C-CD, MnOx@C-D, and MnOx@C-C
Fig.5  Schematic representation of KMnO4 decomposition under DBD
Fig.6  (a) CV curves of MnOx@C-D, MnOx@C-CD, and MnOx@C-C samples in O2-saturated 0.1 mol?L?1 KOH; (b) ORR polarization curves of MnOx@C-D, MnOx@C-CD, and MnOx@C-C at 1600 r?min?1 in O2-saturated 0.1 mol?L?1 KOH
Fig.7  RDE measurements of (a) MnOx@C-D, (b) MnOx@C-C, and (c) MnOx@C-CD at different rotating speeds in O2-saturated 0.1 mol?L?1 KOH; (d) The K-L plots of MnOx@C-D, MnOx@C-C, and commercial 20% Pt/C at ?0.4 V, and MnOx@C-CD at ?0.5 V
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