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One-step synthesis of an octahedral Mn3O4/rGO composite for use as an electrocatalyst in the oxygen reduction reaction

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Abstract

The development of low-cost, high-performance, non-precious-metal catalysts for the oxygen reduction reaction (ORR) is highly desirable. In this work, a composite comprising octahedral manganese oxide supported on reduced graphene oxide (Mn3O4/rGO) was synthesized by a one-step hydrothermal process in the presence of a KMnO4 and graphite oxide (GO) suspension. Importantly, the resulting octahedral Mn3O4/rGO composite exhibits excellent electrocatalytic properties in the ORR. The onset potential of the composite is positively shifted by about 160 and 110 mV compared to those of separate Mn3O4 and rGO, respectively. The corresponding electron transfer number for the ORR catalyzed by Mn3O4/rGO is 3.81, which means that the ORR occurs mainly through a four-electron process. Moreover, the composite shows better stability and tolerance of CH3OH and CO poisoning when compared with a commercial Pt/C catalyst. The superior electrocatalytic performance of the octahedral Mn3O4/rGO composite suggests that it could be an efficient and inexpensive noble-metal-free cathodic catalyst for fuel cells.

A composite comprising octahedral manganese oxide supported on reduced graphene oxide (Mn3O4/rGO) was synthesized using a facile hydrothermal process that did not require an extra reducing agent. The as-prepared Mn3O4/rGO composite exhibits high electrocatalytic activity in the oxygen reduction reaction (ORR). Moreover, the Mn3O4/rGO composite is much more stable than a commercial Pt/C catalyst and is immune to methanol crossover effects

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References

  1. Pickrahn KL, Park SW, Gorlin Y et al (2012) Active MnOx electrocatalysts prepared by atomic layer deposition for oxygen evolution and oxygen reduction reactions. Adv Energy Mater 2:1269–1277

    Article  CAS  Google Scholar 

  2. Gong K, Du F, Xia Z et al (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323:760–764

    Article  CAS  PubMed  Google Scholar 

  3. Gao S, Geng K, Liu H et al (2015) Transforming organic-rich amaranthus waste into nitrogen-doped carbon with superior performance of the oxygen reduction reaction. Energy Environ Sci 8:221–229

    Article  CAS  Google Scholar 

  4. Zhang J, Dai L (2015) Heteroatom-doped graphitic carbon catalysts for efficient electrocatalysis of oxygen reduction reaction. ACS Catal 5:7244–72535

    Article  CAS  Google Scholar 

  5. Zhang Z, Liu J, Gu J et al (2014) An overview of metal oxide materials as electrocatalysts and supports for polymer electrolyte fuel cells. Energy Environ Sci 7:2535

    Article  CAS  Google Scholar 

  6. Babu KJ, Zahoor A, Nahm KS et al (2014) The influences of shape and structure of MnO2 nanomaterials over the non-enzymatic sensing ability of hydrogen peroxide. J Nanopart Res 16:2250

    Article  CAS  Google Scholar 

  7. Cheng F, Shen J, Ji W et al (2009) Selective synthesis of manganese oxide nanostructures for electrocatalytic oxygen reduction. ACS Appl Mater Interfaces 1:460–466

    Article  CAS  PubMed  Google Scholar 

  8. Xiao W, Wang DL, Lou XW (2009) Shape-controlled synthesis of MnO2 nanostructures with enhanced electrocatalytic activity for oxygen reduction. J Phys Chem C 114:1694–1700

    Article  CAS  Google Scholar 

  9. Mao LQ, Zhang D, Sotomura T et al (2003) Mechanistic study of the reduction of oxygen in air electrode with manganese oxides as electrocatalysts. Electrochim Acta 48:1015–1021

    Article  CAS  Google Scholar 

  10. Huang Y, Huang H, Gao Q et al (2014) Electroless synthesis of two-dimensional sandwich-like Pt/Mn3O4/reduced-graphene-oxide nanocomposites with enhanced electrochemical performance for methanol oxidation. Electrochim Acta 149:34–41

    Article  CAS  Google Scholar 

  11. Li CS, Sun Y, Lai WH et al (2016) Ultrafine Mn3O4 nanowires/three-dimensional graphene/single-walled carbon nanotube composites: superior electrocatalysts for oxygen reduction and enhanced Mg/air batteries. ACS Appl Mater Interfaces 8:27710–27719

  12. Jin W, Han X, He Y et al (2016) Galvanic replacement mediated synthesis of rGO–Mn3O4–Pt nanocomposites for the oxygen reduction reaction. RSC Adv 6:89124–89129

    Article  CAS  Google Scholar 

  13. Ahn C, Kalubarme RS, Kim Y et al (2014) Graphene/doped ceria nano-blend for catalytic oxygen reduction in non-aqueous lithium-oxygen batteries. Electrochim Acta 117:18–25

    Article  CAS  Google Scholar 

  14. Şanlı LI, Yarar B, Bayram V et al (2017) Electrosprayed catalyst layers based on graphene–carbon black hybrids for the next-generation fuel cell electrodes. J Mater Sci 52:2091–2102

    Article  CAS  Google Scholar 

  15. Kong D, Yuan W, Li C et al (2017) Synergistic effect of nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction. Appl Surf Sci 393:144–150

    Article  CAS  Google Scholar 

  16. Liu J, Jiang L, Zhang T et al (2016) Activating Mn3O4 by morphology tailoring for oxygen reduction reaction. Electrochim Acta 205:38–44

    Article  CAS  Google Scholar 

  17. Li G, Sun T, Fu Y et al (2016) Graphitic C3N4@MWCNTs supported Mn3O4 as a novel electrocatalyst for the oxygen reduction reaction in zinc–air batteries. J Solid State Electrochem 20:2685–2692

    Article  CAS  Google Scholar 

  18. Su Y, Chai H, Sun Z et al (2016) High-performance manganese nanoparticles on reduced graphene oxide for oxygen reduction reaction. Catal Lett 146:1019–1026

  19. Kong S, Cheng K, Gao Y et al (2016) A novel three-dimensional manganese dioxide electrode for high performance supercapacitors. J Power Sources 308:141–148

    Article  CAS  Google Scholar 

  20. Khalil M, El-Aryan YF, Ali IM (2016) Hydrothermal synthesis of Mn-Fe nano oxides and their composite for removal of Zn2+, Ni2+ and Co2+ from simulated radioactive waste. J Inorg Organomet Polym Mater 26:359–369

  21. Park SK, Jin A, Yu SH et al (2014) In situ hydrothermal synthesis of Mn3O4 nanoparticles on nitrogen-doped graphene as high-performance anode materials for lithium ion batteries. Electrochim Acta 120:452–459

  22. Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339–1339

    Article  CAS  Google Scholar 

  23. Zeng Q, Cheng J, Tang L et al (2010) Self-assembled graphene-enzyme hierarchical nanostructures for electrochemical biosensing. Adv Funct Mater 20:3366–3372

    Article  CAS  Google Scholar 

  24. Li L, Hu Z, Yang Y et al (2013) Hydrothermal self-assembly synthesis of Mn3O4/reduced graphene oxide hydrogel and its high electrochemical performance for supercapacitors. Chin J Chem 31:1290–1298

  25. Lee JW, Hall AS, Kim JD et al (2012) A facile and template-free hydrothermal synthesis of Mn3O4 nanorods on graphene sheets for supercapacitor electrodes with long cycle stability. Chem Mater 24:1158–1164

    Article  CAS  Google Scholar 

  26. Li L, Seng KH, Liu H et al (2013) Synthesis of Mn3O4 anchored graphene sheet nanocomposites via a facile, fast microwave hydrothermal method and their supercapacitive behavior. Electrochim Acta 87:801–808

    Article  CAS  Google Scholar 

  27. Ezeigwe ER, Tan MTT, Khiew PS et al (2015) Solvothermal synthesis of graphene–MnO2 nanocomposites and their electrochemical behavior. Ceram Int 41:11418–11427

    Article  CAS  Google Scholar 

  28. Guo HL, Wang XF, Qian QY et al (2009) A green approach to the synthesis of graphene nanosheets. ACS Nano 3:2653–2659

    Article  CAS  PubMed  Google Scholar 

  29. Chai H, Xu J, Han JI et al (2017) Facile synthesis of Mn3O4-rGO hybrid materials for the high-performance electrocatalytic reduction of oxygen. J Colloid Interface Sci 488:251–257

    Article  CAS  PubMed  Google Scholar 

  30. Bikkarolla SK, Yu F, Zhou W et al (2014) A three-dimensional Mn3O4 network supported on a nitrogenated graphene electrocatalyst for efficient oxygen reduction reaction in alkaline media. J Mater Chem A 2:14493–14501

    Article  CAS  Google Scholar 

  31. Huang D, Zhang B, Li S et al (2014) Mn3O4/carbon nanotube nanocomposites as electrocatalysts for the oxygen reduction reaction in alkaline solution. ChemElectroChem 1:1531–1536

    Article  CAS  Google Scholar 

  32. Chen Y, Qian J, Cao Y et al (2012) Green synthesis and stable Li-storage performance of FeSi2/Si@C nanocomposite for lithium-ion batteries. ACS Appl Mater Interfaces 4:3753–3758

  33. Suhag D, Singh A, Chattopadhyay S et al (2015) Hydrothermal synthesis of nitrogen doped graphene nanosheets from carbon nanosheets with enhanced electrocatalytic properties. RSC Adv 5:39705–39713

    Article  CAS  Google Scholar 

  34. Su Y, Jiang H, Zhu Y et al (2014) Enriched graphitic N-doped carbon-supported Fe3O4 nanoparticles as efficient electrocatalysts for oxygen reduction reaction. J Mater Chem A 2:7281

    Article  CAS  Google Scholar 

  35. Yang Z, Zhou X, Nie H et al (2011) Facile construction of manganese oxide doped carbon nanotube catalysts with high activity for oxygen reduction reaction and investigations into the origin of their activity enhancement. ACS Appl Mater Interfaces 3:2601–2606

    Article  CAS  PubMed  Google Scholar 

  36. Shi C, Zang G, Zhang Z et al (2014) Synthesis of layered MnO2 nanosheets for enhanced oxygen reduction reaction catalytic activity. Electrochim Acta 132:239–243

  37. Hou Y, Wen Z, Cui S et al (2015) An advanced nitrogen-doped graphene/cobalt-embedded porous carbon polyhedron hybrid for efficient catalysis of oxygen reduction and water splitting. Adv Funct Mater 25:872–882

    Article  CAS  Google Scholar 

  38. Mohan N, Cindrella L (2017) Template-free synthesis of Pt-MOx (M= Ni, Co & Ce) supported on cubic zeolite-A and their catalytic role in methanol oxidation and oxygen reduction reactions characterized by the hydrodynamic study. Int J Hydrog Energy 42:21719–21731

  39. Wang MY, Huang JR, Wang M et al (2013) Co3O4 nanorods decorated reduced graphene oxide composite for oxygen reduction reaction in alkaline electrolyte. Electrochem Commun 34:299–303

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (21571034) and the Natural Science Foundation of Fujian Province (2014 J01033).

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Authors and Affiliations

  1. College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian, 350007, China

    Yi Zhang, Xiaofeng Zhang, Meirong Liu, Yuqing Liu, Huodi Huang & Shen Lin

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  1. Yi Zhang
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  2. Xiaofeng Zhang
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  3. Meirong Liu
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  4. Yuqing Liu
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  5. Huodi Huang
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  6. Shen Lin
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Correspondence to Shen Lin.

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Zhang, Y., Zhang, X., Liu, M. et al. One-step synthesis of an octahedral Mn3O4/rGO composite for use as an electrocatalyst in the oxygen reduction reaction. J Solid State Electrochem 22, 2159–2168 (2018). https://doi.org/10.1007/s10008-018-3902-6

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  • DOI: https://doi.org/10.1007/s10008-018-3902-6

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