Cu-based N-doped/undoped graphene nanocomposites as electrocatalysts for the oxygen reduction
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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.
KeywordsCu-based nanocomposites Graphene N-doping Cu–Nx/C active sites Oxygen reduction reaction
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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