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CoMn-LDH@carbon Nanotube Composites: Bifunctional Electrocatalysts For Oxygen Reactions
M. F. Duarte, Inês M. Rocha, J. L. Figueiredo, C. Freire, M. F. R. Pereira
Published 2018 · Chemistry
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Abstract In the present work, a set of five Layered Double Hydroxides, LDH, containing Co and Mn derived electrocatalysts was prepared for the oxygen electrode, evaluating their performances in ORR and OER. A LDH with a Co/Mn ratio of 4, CoMn4, was the reference electrocatalyst of the set, presenting the typical hydrotalcite structure with a trace of MnCo2O4, with a surface area of 76 m2 g−1. HNO3 oxidized carbon nanotubes (CNT_HNO3) and CNT_HNO3 with a low content of carboxylic acids (CNT_ HNO3tt350), were incorporated into the CoMn4 synthesis, obtaining CoMn4@CNT_HNO3 and CoMn4@CNT_HNO3tt350 with surface areas of 111 and 167 m2 g−1, respectively. According to X-ray diffraction (XRD), the oxide phase of CoMn4@CNT_HNO3 is composed by a mixture of LDH with MnCo2O4, while the low%COOH on the carbon surface promoted the synthesis of LDHs as the only oxide structure at CoMn4@CNT_HNO3tt350. Moreover, after a thermal treatment of the latter electrocatalyst, the LDHs were totally converted into MnCo2O4. All electrocatalysts showed to have activity over both oxygen reactions when the KOH solution was saturated with O2. A detailed ORR study showed that the LDH structures mixed with CoMn oxides, present at CoMn4@CNT_HNO3, play a relevant role in ORR, exhibiting an onset potential, EORR, of −0.274 V. On the other hand, CoMn4@CNT_HNO3tt350 led to a four-electron mechanism for ORR, similar to the Pt/C standard. The best OER potential (0.636 V) was also obtained for CoMn4@CNT_HNO3tt350. Regarding the oxygen electrode bifunctionality, a good balance between ORR and OER was observed for the CoMn4@CNT_HNO3tt350_N2 composite.
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