Multivalent manganese oxides with high electrocatalytic activity for oxygen reduction reaction

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.

Key words： oxygen reduction reaction; manganese oxides; mixed valences of manganese; oxygen adsorption; dielectric barrier discharge

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.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-018-1706-y and is accessible for authorized users.

References

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

2 Ben LIEW K, Daud W R W, Ghasemi M, Leong J X, Lim W S, 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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

20 Li Y, Wei Z, Wang Y. 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

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

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

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

24 Wu Q, Jiang M, Zhang X, Cai J, Lin S. 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

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

26 Hosseini-Benhangi P, Kung C H, Alfantazi A, Gyenge E L. Controlling the interfacial environment in the electrosynthesis of MnO_x nanostructures for high-performance oxygen reduction/evolution electrocatalysis. ACS Applied Materials & Interfaces, 2017, 9(32): 26771–26785

27 Chen C F, King G, Dickerson R M, Papin P A, Gupta S, Kellogg W R, Wu G. Oxygen-deficient BaTiO_3‒x perovskite as an efficient bifunctional oxygen electrocatalyst. Nano Energy, 2015, 13: 423–432

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

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

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

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

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

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)

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

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

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

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