Electronic-Structure Transformation of Platinum-Rich Nanowires as Efficient Electrocatalyst for Overall Water Splitting.

Platinum (Pt) has been widely used as cathodic electrocatalysts for the hydrogen evolution reaction (HER) but unfortunately neglected as an anodic electrocatalyst for the oxygen evolution reaction (OER) due to excessively strong bonding with oxygen species in water splitting electrolyzers. Herein we report that fine control over the electronic-structure and local-coordination environment of Pt-rich PtPbCu nanowires (NWs) by doping of iridium (Ir) lowers the overpotential of the OER and simultaneously suppresses the overoxidation of Pt in IrPtPbCu NWs during water electrolysis. In light of the one-dimensional morphology featured with atomically dispersed IrO species and electronically modulated Pt-sites, the IrPtPbCu NWs exhibit an enhanced OER (175 mV at 10 mA cm) and HER (25 mV at 10 mA cm) electrocatalytic performance in acidic media and yield a high turnover frequency. For OER at the overpotential of 250 mV, the IrPtPbCu NWs show an enhanced mass activity of 1.51 A mg (about 19 times higher) than Ir/C. For HER at the overpotential of 50 mV, NWs exhibit a remarkable mass activity of 1.35 A mg, which is 2.6-fold relative to Pt/C. Experimental results and theoretical calculations corroborate that the doping of Ir in NWs has the capacity to suppress the formation of Pt derivates and ameliorate the adsorption free energy of reaction intermediates during the water electrolysis. This approach enabled the realization of a previously unobserved mechanism for anodic electrocatalysts.