La1.5Sr0.5NiMn0.5Ru0.5O6 Double Perovskite with Enhanced ORR/OER Bifunctional Catalytic Activity.

ABSTRACT

Perovskites (ABO3) with transition metals in active B sites are considered alternative catalysts for the water oxidation to oxygen through the oxygen evolution reaction (OER) and for the oxygen reduction through the oxygen reduction reaction (ORR) back to water. We have synthesized a double perovskite (A2BB'O6) with different cations in A, B, and B' sites, namely, (La1.5Sr0.5)A(Ni0.5Mn0.5)B(Ni0.5Ru0.5)B'O6 (LSNMR), which displays an outstanding OER/ORR bifunctional performance. The composition and structure of the oxide has been determined by powder X-ray diffraction, powder neutron diffraction, and transmission electron microscopy to be monoclinic with the space group P21/ n and with cationic ordering between the ions in the B and B' sites. X-ray absorption near-edge spectroscopy suggests that LSNMR presents a configuration of ∼Ni2+, ∼Mn4+, and ∼Ru5+. This bifunctional catalyst is endowed with high ORR and OER activities in alkaline media, with a remarkable bifunctional index value of ∼0.83 V (the difference between the potentials measured at -1 mA cm-2 for the ORR and +10 mA cm-2 for the OER). The ORR onset potential ( Eonset) of 0.94 V is among the best reported to date in alkaline media for ORR-active perovskites. The ORR mass activity of LSNMR is 1.1 A g-1 at 0.9 V and 7.3 A g-1 at 0.8 V. Furthermore, LSNMR is stable in a wide potential window down to 0.05 V. The OER potential to achieve a current density of 10 mA cm-2 is 1.66 V. Density functional theory calculations demonstrate that the high ORR/OER activity of LSNMR is related to the presence of active Mn sites for the ORR- and Ru-active sites for the OER by virtue of the high symmetry of the respective reaction steps on those sites. In addition, the material is stable to ORR cycling and also considerably stable to OER cycling.