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Cu-based N-doped/undoped graphene nanocomposites as electrocatalysts for the oxygen reduction

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Abstract

The development of efficient electrocatalysts for the energy-related reactions, based on earth-abundant elements, is extremely important for a sustainable energetic future. Herein, we report the application of Cu nanoparticles supported on undoped and N-doped graphene—Cu/GOE and Cu/GOE-u composites, respectively—as electrocatalysts for the oxygen reduction reaction (ORR). All the materials showed ORR electrocatalytic activities in alkaline medium. The Cu/GOE-u composite exhibited the most promising performance, with an onset potential of 0.84 V and a current density of jL = − 4.4 mA cm−2 (vs. 0.84 V and − 2.8 mA cm−2 for Cu/GOE), which revealed the great influence of the created Cu–Nx/C active sites on the ORR electrocatalytic activity. The pure GOE-u support showed worse performance than the GOE, demonstrating that the N-doping advantage is not linear and also depends on the type and amount of accessible active sites created. The N-doping allowed an increase in the selectivity for the 4-electron process, resulting in a % of H2O2 produced < 25% for Cu/GOE-u (vs. almost 75% for Cu/GOE). Both nanocomposites revealed good tolerance to methanol crossover, and the Cu/GOE-u displayed a moderate long-term electrochemical stability, with current retention of 84% after 20,000 s.

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Acknowledgements

This work was co-financed by Fundação para a Ciência e a Tecnologia (FCT)/MEC and EU under FEDER founds (Grant No. POCI/01/0145/FEDER/007265) and Programme PT2020 (Project UID/QUI/50006/2013), Project Charphite—ERAMIN/0006/2015—and by Project UNIRCELL—POCI-01-0145-FEDER-016422—funded by European Structural and Investment Funds (FEEI) through—Programa Operacional Competitividade e Internacionalização—COMPETE2020.

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Authors and Affiliations

  1. REQUIMTE/LAQV, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, 4169-007, Porto, Portugal

    Marta Nunes, Diana M. Fernandes & Cristina Freire

  2. Instituto de Catálisis y Petroleoquímica, CSIC, C/Marie Curie 2, Cantoblanco, 28049, Madrid, Spain

    M. V. Morales & I. Rodríguez-Ramos

  3. Departamento de Química Inorgánica y Química Técnica, Facultad de Ciencias, UNED, Senda del Rey 9, 28040, Madrid, Spain

    A. Guerrero-Ruiz

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  1. Marta Nunes
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  2. Diana M. Fernandes
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  3. M. V. Morales
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Nunes, M., Fernandes, D.M., Morales, M.V. et al. Cu-based N-doped/undoped graphene nanocomposites as electrocatalysts for the oxygen reduction. J Appl Electrochem 49, 693–703 (2019). https://doi.org/10.1007/s10800-019-01317-y

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