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Electrochemical behavior of europium perovskites (Ca0.6Eu0.4MnO3) in alkaline aqueous media

Journal of Solid State Electrochemistry volume 20, pages 1713–1722 (2016)Cite this article

Abstract

In this paper, the electrochemical behavior of europium perovskites (Ca0.6Eu0.4MnO3) prepared by a gel combustion method followed by a thermal treatment performed at 1073 and 1473 K is compared with the pristine oxide CaMnO3 (T = 1073 K) obtained by the same method. The experiments were performed in alkaline aqueous media via open-circuit potential, cyclic voltammetry, chronopotentiometry, and impedance spectroscopy. The data show that the electrode roughness is inversely proportional to the oxide particle size. The chronopotentiometric curves show also that the presence of europium is advantageous due to the increase of the electrode roughness for the oxides formed at the same temperature (1073 K) or by increasing the charge per unit area for the oxide formed at 1473 K. The impedance spectra, which were obtained in the capacitive behavior domain, reflect the porous morphology of the electrode surfaces according to the theory developed by Levie. This feature is particularly evident for the electrodes with an average particle diameter of 90 and 60 nm, corresponding respectively to the oxides CaMnO3 and Ca0.6Eu0.4MnO3, both formed at 1073 K.

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References

  1. Ni C, Irvine JTS (2015) Calcium manganite as oxygen electrode materials for reversible solid oxide fuel cell. Faraday Discuss 182:289–305

    Article  CAS  Google Scholar 

  2. Lay E, Benamira M, Pirovano C, Gauthier G, Dessemond L (2012) Effect of Ce-doping on the electrical and electrocatalytical behaviour of La/Sr chromo-manganite perovskite as new SOFC anode. Fuel Cells 12:265–274

    Article  CAS  Google Scholar 

  3. Marina OA, Pederson LR, Williams MC, Coffey GW, Meinhardtn KD, Nguyen CD, Thomsen EC (2007) Electrode performance in reversible solid oxide fuel cells. J Electrochem Soc 154:B452–B459

    Article  CAS  Google Scholar 

  4. Bernuy-Lopez C, Knibbe R, He Z, Mao X, Hauch A, Nielsen KA (2011) Electrochemical characterization of solid oxide cell electrodes for hydrogen production. J Power Sources 196:4396–4403

    Article  CAS  Google Scholar 

  5. Morimoto H, Esaka T, Takai S (1997) Properties of the perovskite-type oxide ceramic Ca1-x La2x/3MnO3-δ as the cathode active materials in alkaline batteries. Mater Res Bull 32:1359–1366

    Article  CAS  Google Scholar 

  6. Esaka T, Adachi Y (2014) Electrode property of sintered ceramic based on CaMnO3 in LiOH aqueous solution. J Mater Sci Chem Eng 2:15–21

    CAS  Google Scholar 

  7. Zhang K, Han X, Hu Z, Zhang X, Tao Z, Chen J (2015) Nanostructured Mn-based oxides for electrochemical energy storage and conversion. Chem Soc Rev 44:699–728

    Article  CAS  Google Scholar 

  8. Han X, Hu Y, Yang J, Cheng F, Chen J (2014) Porous perovskite CaMnO3 as an electrocatalyst for rechargeable Li–O2 batteries. Chem Commun 50:1497–1499

    Article  CAS  Google Scholar 

  9. Fu Z, Lin X, Huang T, Yu A (2012) Nano-Sized La0.8Sr0.2MnO3 as oxygen reduction catalyst in nonaqueous Li/O2 batteries. J Solid State Electrochem 16:1497–1452

    Article  Google Scholar 

  10. Li G, Zhang K, Mezaal MA, Lei L (2015) Synthesis and electrochemical evaluation of La1−x Sr x MnO3 catalysts for zinc-air batteries. J Solid State Electrochem. doi:10.1007/s10008-015-3056-8

    Google Scholar 

  11. Li G, Mezzal MA, Zhang R, Zhang K, Liu W, Lei L (2015) Electrochemical evaluation of La1−x Sr x MnO3 in zinc-air batteries. Int J Electrochem Sci 10:8412–8422

    CAS  Google Scholar 

  12. Du J, Zhang T, Cheng F, Chu W, Wu Z, Chen J (2014) Nonstoichiometric perovskite CaMnO3−δ for oxygen electrocatalysis with high activity. J Inorg Chem 53:9106–9114

    Article  CAS  Google Scholar 

  13. Raabe S, Meirwaldt D, Ciston J, Uijttewaal M, Stein H, Hoffman J, Zhu Y, Blöchl P, Jooss C (2012) In situ electrochemical electron microscopy study of oxygen evolution activity of doped manganite perovskites. Adv Funct Mater 22:3378–3388

    Article  CAS  Google Scholar 

  14. Suntivivh J, May KJ, Gasteiger HA, Goodenough JB, Shao-Horn Y (2011) A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334:1383–1385

    Article  Google Scholar 

  15. Mierwaldt D, Mildner S, Arrigo R, Knop-Gericke A, Franke E, Blumenstein A, Hoffmann J, Jooss C (2014) In situ XANES/XPS investigation of doped manganese perovskite catalysts. Catal 4:129–145

    Article  Google Scholar 

  16. Han X, Cheng F, Zhang T, Jingang Y, Hu Y, Chen J (2014) Hydrogenated uniform Pt clusters supported on porous CaMnO3 as a bifunctional electrocatalyst for enhanced oxygen reduction and evolution. Adv Mater 26:2047–2051

    Article  CAS  Google Scholar 

  17. Peña MA, Fierro JLG (2001) Chemical structures and performance of perovskite oxides. Chem Rev 101:1981–2017

    Article  Google Scholar 

  18. Melo Jorge ME, Nunes MR, Silva Maria R, Sousa D (2005) Insulator-metal transition induced by Ce doping in CaMnO3. Chem Mater 17:2069–2075

    Article  Google Scholar 

  19. Isasi PH, Lopes ME, Nunes MR, Melo Jorge ME (2009) Low-temperature synthesis of nanocrystalline Ca1-x Ho x MnO3-δ (0 < x < 0.3) powders. J Phys Chem Solids 70:405–411

    Article  CAS  Google Scholar 

  20. Matos I, Sério S, Lopes ME, Nunes MR, Melo Jorge ME (2011) Effect of the sintering temperature on the properties of nanocrystalline Ca1-x Sm x MnO3 (0 ≤ x ≤ 0.4) powders. J Alloys Compds 509:9617–9626

    Article  CAS  Google Scholar 

  21. Silveira C, Lopes ME, Nunes MR, Melo Jorge ME (2010) Synthesis and electrical properties of nanocrystalline Ca1−x Eu x MnO3±δ (0.1 ≤ x ≤ 0.4) powders prepared at low temperature using citrate gel method. Solid State Ionics 180:1702–1709

    Article  CAS  Google Scholar 

  22. Sousa D, Nunes MR, Lopes AB, Melo Jorge ME (2008) Ca-site doping induced a metal-insulator transition in manganite CaMnO3. Mater Chem Phys 109:311–319

    Article  CAS  Google Scholar 

  23. Najjar H, Batis H, Lamonier JF, Mentréa O, Giraudon JM (2014) Effect of praseodymium and europium doping in La1−x LnxMnO3+ı (ln: Pr or Eu, 0 ≤ x ≤ 1) perosvkite catalysts for total methane oxidation. Appl Catal A Gen 469:98–107

    Article  CAS  Google Scholar 

  24. Phuruangrat A, Yayapao O, Thongtem T, Thongtem S (2014) Synthesis and characterization of europium-doped zinc oxide photocatalyst. J Nanomaterials 2014:(Article ID 367529), 9 pages

  25. Zhao Y, Zhang C, Liu T, Du ZJ, Liang S, Wang X (2012) Electrocatalytic activity of europium doped tantalum oxide for ascorbic acid oxidation in aqueous. Int J Electrochem Sci 7:6417–6425

    CAS  Google Scholar 

  26. Moustafa MSA (ed) (2013) Europium: synthesis, characteristics and potential applications. Nova Science publishers, New York

    Google Scholar 

  27. Melo Jorge ME, Correia dos Santos A, Nunes MR (2001) Effects of synthesis method on stoichiometry, structure and electrical conductivity of CaMnO3-δ. Int J Inorg Mater 3:915–921

    Article  Google Scholar 

  28. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A: Found Crystallogr 32:751–767

    Article  Google Scholar 

  29. Pourbaix M (1974) Atlas of electrochemical equilibria in aqueous solutions. NACE, Houston

    Google Scholar 

  30. Ferreira BM, Melo Jorge ME, Lopes ME, Nunes MR, Silva Pereira MI (2009) Properties of Ca1-x Ho x MnO3 perovskite-tipe electrodes. Electrochim Acta 54:5902–5908

    Article  CAS  Google Scholar 

  31. Barrocas B, Sério S, Rovisco A, Nunes Y, Sá AI, Silva Pereira MI, Melo Jorge ME (2014) Characterization and electrochemical behaviour of nanostructured calcium samarium manganite electrodes fabricated by RF-magnetron sputtering. Electrochim Acta 137:99–107

    Article  CAS  Google Scholar 

  32. Lucas C, Eiroa I, Nunes MR, Russo PA, Ribeiro Carrott MML, Silva Pereira MI, Melo Jorge ME (2009) Preparation and characterization of Ca1-x Ce x MnO3 perovskite electrodes. J Solid State Electrochem 13:943–950

    Article  CAS  Google Scholar 

  33. Bockris LOM, Sum K (1993) Surface electrochemistry, a molecular level approach. Plenum, New York

    Book  Google Scholar 

  34. Silva LM, Faria LA, Boodts JFC (2001) Determination of the morphology factor of oxide layers. Electrochim Acta 47:395–403

    Article  Google Scholar 

  35. Levine S, Smith AL (1971) Theory of the differential capacity of the oxide/aqueous electrolyte interface. Discuss Faraday Soc 52:290–301

    Article  Google Scholar 

  36. Greef R, Peat R, Peter LM, Pletcher D, Ronbison J (1985) Instrumental methods in electrochemistry. Ellis Horwood Lmd, Chichester

    Google Scholar 

  37. Brett AMO, Brett CMA (1993) Electrochemistry: principles, methods and applications. Oxford University Press, Oxford

    Google Scholar 

  38. Levie R (1963) On porous electrodes in electrolyte solutions: I. capacitance effects. Electrochim Acta 8:751–780

    Article  Google Scholar 

  39. Chen L, Lasia A (1993) Ni-Al powder electrocatalyst for hydrogen evolution. J Electrochem Soc 140:2464–2473

    Article  CAS  Google Scholar 

  40. Hitz C, Lasia A (2001) Experimental study and modeling of impedance of the her on porous Ni electrodes. J Electroanal Chem 500:213–222

    Article  CAS  Google Scholar 

  41. Jurczakowski R, Hitz C, Lasia A (2004) Impedance of porous Au based electrodes. J Electroanal Chem 572:355–366

    Article  CAS  Google Scholar 

  42. Valek L, Metikos-Hukovic M, Grubac Z (2006) Impedance spectroscopy characterization of the electrodeposited Ni-15Mo catalyst designed for the HER in acid solution: modified porous model. J New Mat Electr Sys 9:145–153

    CAS  Google Scholar 

  43. Burg GJ, Eeden ALG, Sluyters-Rehbach M, Sluyters JH (1984) The analysis of electrode impedances complicated by the presence of a constant phase element. J Electroanal Chem 176:275–295

    Article  Google Scholar 

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Acknowledgments

M.E. Melo Jorge thanks Fundação para a Ciência e Tecnologia (FCT) for funding (UID/MULTI/00612/2013). Acknowledgments are also due to Laboratório Nacional de Energia e Geologia (LNEG) in the framework of the MESOPOROUS project.

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Authors and Affiliations

  1. Unidade de Energia Solar, Laboratório Nacional de Energia e Geologia, Paço do Lumiar 22, 1649-038, Lisboa, Portugal

    A. I. de Sá & C. M. Rangel

  2. Centro de Química e Bioquímica, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande C8, 1749-016, Lisboa, Portugal

    M. E. Melo Jorge

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  1. A. I. de Sá
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Correspondence to A. I. de Sá.

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de Sá, A.I., Rangel, C.M. & Jorge, M.E.M. Electrochemical behavior of europium perovskites (Ca0.6Eu0.4MnO3) in alkaline aqueous media. J Solid State Electrochem 20, 1713–1722 (2016). https://doi.org/10.1007/s10008-016-3184-9

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