Mn doped CoFe layered double hydroxides lead to d-d orbital repulsion toward advanced electrocatalysts for oxygen evolution reaction

Currently, developing highly active and low-cost electrocatalytic materials for oxygen evolution reaction (OER) is an enormously grand challenge. Herein, we developed a novel and highly active Mn doped Co 2 Fe layer double hydroxide (LDH) electrocatalyst for OER. We discovered that these electrocatalytic materials can be directly grown on carbon papers to construct high-specific-surface-area electrode, which shows the lowest overpotential of 266 mV at 10 mA cm −2 . Furthermore, after introducing Mn element, DFT + U calculation found that the ∗OOH of Fe-site on Co 2 Fe 0.67 Mn 0.33 LDH could draw more electrons than Co 2 Fe LDH due to the electronegativity differences between Fe-site on Co 2 Fe 0.67 Mn 0.33 LDH and Fe-site on Co 2 Fe LDH, which is reason that the energy level of Fe 3d (e g ) was obviously downshifted by d-d repulsion of Mn 3d and Fe 3d in the neighboring sites of Co 2 Fe 0.67 Mn 0.33 LDH after doped Mn element, which leads to reduce charge-transfer energy from O 2p to Fe 3d (e g ) to promote oxygen evolution processes for OER. Meanwhile, the band gap is also decreased after doped Mn element in Co 2 Fe LDH due to the downshifted e g orbital energy of Fe 3d. This study gives a general avenue to design and developing efficiently active LDH electrocatalysts for OER in the future.