Skip to main content
SpringerLink
Log in

Multivalent manganese oxides with high electrocatalytic activity for oxygen reduction reaction

  • Research Article
  • Published:
Frontiers of Chemical Science and Engineering Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Chen Z, Higgins D, Yu A, Zhang L, Zhang J. A review on nonprecious metal electrocatalysts for PEM fuel cells. Energy & Environmental Science, 2011, 4(9): 3167–3192

    Article  CAS  Google Scholar 

  2. Ben L K, DaudWR W, Ghasemi M, Leong J X, Lim WS, Ismail M. Non-Pt catalyst as oxygen reduction reaction in microbial fuel cells: A review. International Journal of Hydrogen Energy, 2014, 39(10): 4870–4883

    Article  CAS  Google Scholar 

  3. Xia W, Mahmood A, Liang Z, Zou R, Guo S. Earth-abundant nanomaterials for oxygen reduction. Angewandte Chemie International Edition, 2016, 55(8): 2650–2676

    Article  CAS  PubMed  Google Scholar 

  4. Liao M, Li W, Xi X, Luo C, Fu Y, Gui S, Mai Z, Yan H, Jiang C. Highly active Pt decorated Pd/C nanocatalysts for oxygen reduction reaction. International Journal of Hydrogen Energy, 2017, 42(38): 24090–24098

    Article  CAS  Google Scholar 

  5. Xiong X, Chen W, Wang W, Li J, Chen S. Pt-Pd nanodendrites as oxygen reduction catalyst in polymer-electrolyte-membrane fuel cell. International Journal of Hydrogen Energy, 2017, 42(40): 25234–25243

    Article  CAS  Google Scholar 

  6. An B, Li M, Wang J, Li C. Shape/size controlling syntheses, properties and applications of two-dimensional noble metal nanocrystals. Frontiers of Chemical Science and Engineering, 2016, 10(3): 360–382

    Article  CAS  Google Scholar 

  7. Wu Z, Iqbal Z, Wang X. Metal-free, carbon-based catalysts for oxygen reduction reactions. Frontiers of Chemical Science and Engineering, 2015, 9(3): 280–294

    Article  CAS  Google Scholar 

  8. Lee S, Nam G, Sun J, Lee J, Lee H, Chen W, Cho J, Cui Y. Enhanced intrinsic catalytic activity of lambda-MnO2 by electrochemical tuning and oxygen vacancy generation. Angewandte Chemie International Edition, 2016, 55(30): 8599–8604

    Article  CAS  PubMed  Google Scholar 

  9. El-Deab M S, Ohsaka T. 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

    Article  CAS  Google Scholar 

  10. Chai H, Xu J, Han J, Su Y, Sun Z, Jia D, Zhou W. 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

    Article  CAS  PubMed  Google Scholar 

  11. Gorlin Y, Chung C, Nordlund D, Clemens B M, Jaramillo T F. Mn3O4 supported on glassy carbon: An active non-precious metal catalyst for the oxygen reduction reaction. ACS Catalysis, 2012, 2 (12): 2687–2694

    Article  CAS  Google Scholar 

  12. Vigil J A, Lambert T N, Eldred K. Electrodeposited MnOx/PEDOT composite thin films for the oxygen reduction reaction. ACS Applied Materials & Interfaces, 2015, 7(41): 22745–22750

    Article  CAS  Google Scholar 

  13. Guo S, Lu G, Qiu S, Liu J, Wang X, He C, Wei H, Yan X, Guo Z. Carbon-coated MnO microparticulate porous nanocomposites serving as anode materials with enhanced electrochemical performances. Nano Energy, 2014, 9: 41–49

    Article  CAS  Google Scholar 

  14. Wu X, Gao X, Xu L, Huang T, Yu J, Wen C, Chen Z, Han J. Mn2O3 doping induced the improvement of catalytic performance for oxygen reduction of MnO. International Journal of Hydrogen Energy, 2016, 41(36): 16087–16093

    Article  CAS  Google Scholar 

  15. Guo D, Dou S, Li X, Xu J, Wang S, Lai L, Liu H, Ma J, Dou S. Hierarchical MnO2/rGO hybrid nanosheets as an efficient electrocatalyst for the oxygen reduction reaction. International Journal of Hydrogen Energy, 2016, 41(10): 5260–5268

    Article  CAS  Google Scholar 

  16. Ge X, Du Y, Li B, Hor T S A, Sindoro M, Zong Y, Zhang H, Liu Z. Intrinsically conductive perovskite oxides with enhanced stability and electrocatalytic activity for oxygen reduction reactions. ACS Catalysis, 2016, 6(11): 7865–7871

    Article  CAS  Google Scholar 

  17. Sun S, Miao H, Xue Y, Wang Q, Li S, Liu Z. Oxygen reduction reaction catalysts of manganese oxide decorated by silver nanoparticles for aluminum-air batteries. Electrochimica Acta, 2016, 214: 49–55

    Article  CAS  Google Scholar 

  18. Su Y, Chai H, Sun Z, Liu T, Jia D, Zhou W. High-performance manganese nanoparticles on reduced graphene oxide for oxygen reduction reaction. Catalysis Letters, 2016, 146(6): 1019–1026

    Article  CAS  Google Scholar 

  19. Gao Y, Zhao H, Chen D, Chen C, Ciucci F. 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

    Article  CAS  Google Scholar 

  20. Li Y, Wei Z, Wang Y. Ni/MgO catalyst prepared via dielectricbarrier discharge plasma with improved catalytic performance for carbon dioxide reforming of methane. Frontiers of Chemical Science and Engineering, 2014, 8(2): 133–140

    Article  CAS  Google Scholar 

  21. Han X, Zhang T, Du J, Cheng F, Chen J. Porous calcium-manganese oxide microspheres for electrocatalytic oxygen reduction with high activity. Chemical Science (Cambridge), 2013, 4(1): 368–376

    Article  CAS  Google Scholar 

  22. Bag S, Roy K, Gopinath C S, Raj C R. 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

    Article  CAS  Google Scholar 

  23. Kong D, Yuan W, Li C, Song J, Xie A, Shen Y. Synergistic effect of nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction. Applied Surface Science, 2017, 393: 144–150

    Article  CAS  Google Scholar 

  24. Wu Q, Jiang M, Zhang X, Cai J, Lin S. A novel octahedral MnO/ RGO composite prepared by thermal decomposition as a noblemetal free electrocatalyst for ORR. Journal of Materials Science, 2017, 52(11): 6656–6669

    Article  CAS  Google Scholar 

  25. Biesinger M C, Payne B P, Grosvenor A P, Lau L W M, Gerson A R, Smart R S C. 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

    Article  CAS  Google Scholar 

  26. Hosseini-Benhangi P, Kung C H, Alfantazi A, Gyenge E L. 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

    Article  CAS  Google Scholar 

  27. Chen C F, King G, Dickerson R M, Papin P A, Gupta S, Kellogg W R, Wu G. Oxygen-deficient BaTiO3–x perovskite as an efficient bifunctional oxygen electrocatalyst. Nano Energy, 2015, 13: 423–432

    Article  CAS  Google Scholar 

  28. Cheng G, Xie S, Lan B, Zheng X, Ye F, Sun M, Lu X, Yu L. 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

    Article  CAS  Google Scholar 

  29. Liu K, Lei Y, Wang G. Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes. Journal of Chemical Physics, 2013, 139(20): 204306

    Article  CAS  PubMed  Google Scholar 

  30. Yu M, Wang Z, Hou C, Wang Z, Liang C, Zhao C, Tong Y, Lu X, Yang S. 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

    Article  CAS  Google Scholar 

  31. Song W, Ren Z, Chen S, Meng Y, Biswas S, Nandi P, Elsen H, Gao P, Suib S. 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

    Article  CAS  Google Scholar 

  32. Fang M, Wang Z, Liu C. Characterization and application of Au nanoparticle/agarose composite film fabricated by room temperature electron reduction. Acta Physico-Chimica Sinica, 2017, 33(2): 435–440

    CAS  Google Scholar 

  33. Wang W, Wang Z, Wang J, Zhong C, Liu C. 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)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  34. Lima F H B, Calegaro M L, Ticianelli E A. 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

    Article  CAS  Google Scholar 

  35. Lima F H B, Calegaro M L, Ticianelli E A. Electrocatalytic activity of manganese oxides prepared by thermal decomposition for oxygen reduction. Electrochimica Acta, 2007, 52(11): 3732–3738

    Article  CAS  Google Scholar 

  36. Cheng F, Shen J, Ji W, Tao Z, Chen J. Selective synthesis of manganese oxide nanostructures for electrocatalytic oxygen reduction. ACS Applied Materials & Interfaces, 2009, 1(2): 460–466

    Article  CAS  Google Scholar 

  37. Zhou Y, Lu Q, Zhuang Z, Hutchings G S, Kattel S, Yan Y, Chen J, John Q, Jiao F. Oxygen reduction at very low overpotential on nanoporous Ag catalysts. Advanced Energy Materials, 2015, 5(13): 1500149

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The supports from the National Key Research and Development Program of China (No. 2016YFF0102503), and Tianjin Municipal Natural Science Foundation (No. 16JCYBJC19500) are greatly appreciated.

Author information

Authors and Affiliations

  1. School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin, 300350, China

    Xiangfeng Peng, Zhenhai Wang & Zhao Wang

  2. School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei, 230009, China

    Yunxiang Pan

Authors
  1. Xiangfeng Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zhenhai Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhao Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yunxiang Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Zhao Wang.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Peng, X., Wang, Z., Wang, Z. et al. Multivalent manganese oxides with high electrocatalytic activity for oxygen reduction reaction. Front. Chem. Sci. Eng. 12, 790–797 (2018). https://doi.org/10.1007/s11705-018-1706-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11705-018-1706-y

Keywords

Search

Navigation