Tuning Ir d-orbital occupation via doping Cu into the IrO ₂ lattice to prepare a highly efficient oxygen evolution reaction catalyst, Cu _0.3 Ir _0.7 O _δ .

The anodic reaction of oxygen evolution reaction (OER), an important point for electrolysis, however, remains the obstacle due to its complicated reaction at electrochemical interfaces. Iridium oxide (IrO₂) is the only currently known 5d transition metal oxide possessing admirable OER activity. Tremendous efforts have been carried out to enhance the activity of iridium oxides. Unfortunately there lies a gap in understanding what factors responsible for the activity in doped IrO₂ or the novel crystal structure. Based on two metallic pyrochlores (Bi₂Ir₂O₇ and Pb₂Ir₂O_6.5) and IrO₂. It has been found that there exists a strong correlation between the specific OER activity and IrO₆ coordination geometry. The more distortion in IrO₆ geometry ascends the activity of Ir sites, and generates activity order of Pb-Ir > IrO₂ > Bi-Ir. Our characterizations reveal that distorted IrO₆ in Pb-Ir induces a disappearance of J = 1/2 subbands in valence band, while Bi-Ir and IrO₂ resist this nature probe. The performed DFT calculations indicated the distortion in IrO₆ geometry can optimize binding strength between Ir-5d and O-2p due to broader d band width. Based on this insight, enhancement in OER activity is obtained by effects that change IrO₆ octahedral geometry through doping or utilizing structural manipulation with nature of distorted octahedral coordination.