Please wait a minute...

Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2018, Vol. 12 Issue (4) : 790-797     https://doi.org/10.1007/s11705-018-1706-y
RESEARCH ARTICLE
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
Download: PDF(428 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

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.
 URL:  
http://journal.hep.com.cn/fcse/EN/10.1007/s11705-018-1706-y
http://journal.hep.com.cn/fcse/EN/Y2018/V12/I4/790
Service
E-mail this article
E-mail Alert
RSS
Articles by authors
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
1 ZChen, D Higgins, AYu, LZhang, JZhang. A review on non-precious metal electrocatalysts for PEM fuel cells. Energy & Environmental Science, 2011, 4(9): 3167–3192
https://doi.org/10.1039/c0ee00558d
2 KBen LIEW, W R W Daud, M Ghasemi, J XLeong, W SLim, MIsmail. Non-Pt catalyst as oxygen reduction reaction in microbial fuel cells: A review. International Journal of Hydrogen Energy, 2014, 39(10): 4870–4883
https://doi.org/10.1016/j.ijhydene.2014.01.062
3 WXia, A Mahmood, ZLiang, RZou, S Guo. Earth-abundant nanomaterials for oxygen reduction. Angewandte Chemie International Edition, 2016, 55(8): 2650–2676
https://doi.org/10.1002/anie.201504830
4 MLiao, W Li, XXi, CLuo, Y Fu, SGui, ZMai, H Yan, CJiang. Highly active Pt decorated Pd/C nanocatalysts for oxygen reduction reaction. International Journal of Hydrogen Energy, 2017, 42(38): 24090–24098
https://doi.org/10.1016/j.ijhydene.2017.08.003
5 XXiong, W Chen, WWang, JLi, S Chen. Pt-Pd nanodendrites as oxygen reduction catalyst in polymer-electrolyte-membrane fuel cell. International Journal of Hydrogen Energy, 2017, 42(40): 25234–25243
https://doi.org/10.1016/j.ijhydene.2017.08.162
6 BAn, M Li, JWang, CLi. Shape/size controlling syntheses, properties and applications of two-dimensional noble metal nanocrystals. Frontiers of Chemical Science and Engineering, 2016, 10(3): 360–382
https://doi.org/10.1007/s11705-016-1576-0
7 ZWu, Z Iqbal, XWang. Metal-free, carbon-based catalysts for oxygen reduction reactions. Frontiers of Chemical Science and Engineering, 2015, 9(3): 280–294
https://doi.org/10.1007/s11705-015-1524-4
8 SLee, G Nam, JSun, JLee, H Lee, WChen, JCho, Y Cui. Enhanced intrinsic catalytic activity of lambda-MnO2 by electrochemical tuning and oxygen vacancy generation. Angewandte Chemie International Edition, 2016, 55(30): 8599–8604
https://doi.org/10.1002/anie.201602851
9 M SEl-Deab, T Ohsaka. Electrosynthesis of single-crystalline MnOOH nanorods onto Pt electrodes—electrocatalytic activity toward reduction of oxygen. Journal of the Electrochemical Society, 2008, 155(1): D14–D21
https://doi.org/10.1149/1.2799584
10 HChai, J Xu, JHan, YSu, Z Sun, DJia, WZhou. Facile synthesis of Mn3O4-rGO hybrid materials for the high-performance electrocatalytic reduction of oxygen. Journal of Colloid and Interface Science, 2017, 488: 251–257
https://doi.org/10.1016/j.jcis.2016.10.049
11 YGorlin, C Chung, DNordlund, B MClemens, T FJaramillo. Mn3O4 supported on glassy carbon: An active non-precious metal catalyst for the oxygen reduction reaction. ACS Catalysis, 2012, 2(12): 2687–2694
https://doi.org/10.1021/cs3004352
12 J AVigil, T N Lambert, K Eldred. Electrodeposited MnOx/PEDOT composite thin films for the oxygen reduction reaction. ACS Applied Materials & Interfaces, 2015, 7(41): 22745–22750
https://doi.org/10.1021/acsami.5b07684
13 SGuo, G Lu, SQiu, JLiu, X Wang, CHe, HWei, X Yan, ZGuo. Carbon-coated MnO microparticulate porous nanocomposites serving as anode materials with enhanced electrochemical performances. Nano Energy, 2014, 9: 41–49
https://doi.org/10.1016/j.nanoen.2014.06.025
14 XWu, X Gao, LXu, THuang, JYu, C Wen, ZChen, JHan. Mn2O3 doping induced the improvement of catalytic performance for oxygen reduction of MnO. International Journal of Hydrogen Energy, 2016, 41(36): 16087–16093
https://doi.org/10.1016/j.ijhydene.2016.04.216
15 DGuo, S Dou, XLi, JXu, S Wang, LLai, HLiu, J Ma, SDou. Hierarchical MnO2/rGO hybrid nanosheets as an efficient electrocatalyst for the oxygen reduction reaction. International Journal of Hydrogen Energy, 2016, 41(10): 5260–5268
https://doi.org/10.1016/j.ijhydene.2016.01.070
16 XGe, Y Du, BLi, T S AHor, MSindoro, YZong, H Zhang, ZLiu. Intrinsically conductive perovskite oxides with enhanced stability and electrocatalytic activity for oxygen reduction reactions. ACS Catalysis, 2016, 6(11): 7865–7871
https://doi.org/10.1021/acscatal.6b02493
17 SSun, H Miao, YXue, QWang, S Li, ZLiu. Oxygen reduction reaction catalysts of manganese oxide decorated by silver nanoparticles for aluminum-air batteries. Electrochimica Acta, 2016, 214: 49–55
https://doi.org/10.1016/j.electacta.2016.07.127
18 YSu, H Chai, ZSun, TLiu, D Jia, WZhou. High-performance manganese nanoparticles on reduced graphene oxide for oxygen reduction reaction. Catalysis Letters, 2016, 146(6): 1019–1026
https://doi.org/10.1007/s10562-016-1719-4
19 YGao, H Zhao, DChen, CChen, F Ciucci. In situ synthesis of mesoporous manganese oxide/sulfur-doped graphitized carbon as a bifunctional catalyst for oxygen evolution/reduction reactions. Carbon, 2015, 94: 1028–1036
https://doi.org/10.1016/j.carbon.2015.07.084
20 YLi, Z Wei, YWang. Ni/MgO catalyst prepared via dielectric-barrier discharge plasma with improved catalytic performance for carbon dioxide reforming of methane. Frontiers of Chemical Science and Engineering, 2014, 8(2): 133–140
https://doi.org/10.1007/s11705-014-1422-1
21 XHan, T Zhang, JDu, FCheng, JChen. Porous calcium-manganese oxide microspheres for electrocatalytic oxygen reduction with high activity. Chemical Science (Cambridge), 2013, 4(1): 368–376
https://doi.org/10.1039/C2SC21475J
22 SBag, K Roy, C SGopinath, C RRaj. Facile single-step synthesis of nitrogen-doped reduced graphene oxide-Mn3O4 hybrid functional material for the electrocatalytic reduction of oxygen. ACS Applied Materials & Interfaces, 2014, 6(4): 2692–2699
https://doi.org/10.1021/am405213z
23 DKong, W Yuan, CLi, JSong, A Xie, YShen. Synergistic effect of nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction. Applied Surface Science, 2017, 393: 144–150
https://doi.org/10.1016/j.apsusc.2016.10.019
24 QWu, M Jiang, XZhang, JCai, S Lin. A novel octahedral MnO/RGO composite prepared by thermal decomposition as a noble-metal free electrocatalyst for ORR. Journal of Materials Science, 2017, 52(11): 6656–6669
https://doi.org/10.1007/s10853-017-0901-4
25 M CBiesinger, B PPayne, A PGrosvenor, L W MLau, A RGerson, R S CSmart. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Applied Surface Science, 2011, 257(7): 2717–2730
https://doi.org/10.1016/j.apsusc.2010.10.051
26 PHosseini-Benhangi, C HKung, AAlfantazi, E LGyenge. Controlling the interfacial environment in the electrosynthesis of MnOx nanostructures for high-performance oxygen reduction/evolution electrocatalysis. ACS Applied Materials & Interfaces, 2017, 9(32): 26771–26785
https://doi.org/10.1021/acsami.7b05501
27 C FChen, G King, R MDickerson, P APapin, SGupta, W RKellogg, GWu. Oxygen-deficient BaTiO3‒x perovskite as an efficient bifunctional oxygen electrocatalyst. Nano Energy, 2015, 13: 423–432
https://doi.org/10.1016/j.nanoen.2015.03.005
28 GCheng, S Xie, BLan, XZheng, FYe, M Sun, XLu, LYu. Phase controllable synthesis of three-dimensional star-like MnO2 hierarchical architectures as highly efficient and stable oxygen reduction electrocatalysts. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2016, 4(42): 16462–16468
https://doi.org/10.1039/C6TA04530H
29 KLiu, Y Lei, GWang. Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes. Journal of Chemical Physics, 2013, 139(20): 204306
30 MYu, Z Wang, CHou, ZWang, C Liang, CZhao, YTong, X Lu, S.Yang Nitrogen-doped Co3O4 mesoporous nanowire arrays as an additive-free air-cathode for flexible solid-state zinc-air batteries. Advanced materials, 2017, 29(15): 1602868
31 WSong, Z Ren, SChen, YMeng, S Biswas, PNandi, HElsen, PGao, S Suib. Ni- and Mn-Promoted mesoporous Co3O4: A stable bifunctional catalyst with surface-structure-dependent activity for oxygen reduction reaction and oxygen evolution reaction. ACS Applied Materials & Interfaces, 2016, 8(32): 20802–20813
https://doi.org/10.1021/acsami.6b06103
32 MFang, Z Wang, CLiu. Characterization and application of Au nanoparticle/agarose composite film fabricated by room temperature electron reduction. Acta Physico-Chimica Sinica, 2017, 33(2): 435–440
33 WWang, Z Wang, JWang, CZhong, CLiu. Highly active and stable Pt-Pd alloy catalysts synthesized by room-temperature electron reduction for oxygen reduction reaction. Advanced Science, 2017, 4(4): 1600486(1‒9)
34 F H BLima, M LCalegaro, E ATicianelli. Investigations of the catalytic properties of manganese oxides for the oxygen reduction reaction in alkaline media. Journal of Electroanalytical Chemistry, 2006, 590(2): 152–160
https://doi.org/10.1016/j.jelechem.2006.02.029
35 F H BLima, M LCalegaro, E ATicianelli. Electrocatalytic activity of manganese oxides prepared by thermal decomposition for oxygen reduction. Electrochimica Acta, 2007, 52(11): 3732–3738
https://doi.org/10.1016/j.electacta.2006.10.047
36 FCheng, J Shen, WJi, ZTao, J Chen. Selective synthesis of manganese oxide nanostructures for electrocatalytic oxygen reduction. ACS Applied Materials & Interfaces, 2009, 1(2): 460–466
https://doi.org/10.1021/am800131v
37 YZhou, Q Lu, ZZhuang, G SHutchings, SKattel, YYan, J Chen, QJohn, FJiao. Oxygen reduction at very low overpotential on nanoporous Ag catalysts. Advanced Energy Materials, 2015, 5(13): 1500149
https://doi.org/10.1002/aenm.201500149
[1] FCE-17051-OF-PY_suppl_1 Download
Related articles from Frontiers Journals
[1] Mehraneh Ghavami, Mostafa Aghbolaghy, Jafar Soltan, Ning Chen. Room temperature oxidation of acetone by ozone over alumina-supported manganese and cobalt mixed oxides[J]. Front. Chem. Sci. Eng., 2020, 14(6): 937-947.
[2] Huixin Zhang, Jinying Liang, Bangwang Xia, Yang Li, Shangfeng Du. Ionic liquid modified Pt/C electrocatalysts for cathode application in proton exchange membrane fuel cells[J]. Front. Chem. Sci. Eng., 2019, 13(4): 695-701.
[3] Rusen Zhou, Renwu Zhou, Xianhui Zhang, Kateryna Bazaka, Kostya (Ken) Ostrikov. Continuous flow removal of acid fuchsine by dielectric barrier discharge plasma water bed enhanced by activated carbon adsorption[J]. Front. Chem. Sci. Eng., 2019, 13(2): 340-349.
[4] Minhua Zhang, Baojuan Huang, Haoxi Jiang, Yifei Chen. Metal-organic framework loaded manganese oxides as efficient catalysts for low-temperature selective catalytic reduction of NO with NH3[J]. Front. Chem. Sci. Eng., 2017, 11(4): 594-602.
[5] Zhiyi Wu,Zafar Iqbal,Xianqin Wang. Metal-free, carbon-based catalysts for oxygen reduction reactions[J]. Front. Chem. Sci. Eng., 2015, 9(3): 280-294.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed