Developing highly efficient and low-cost bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting poses significant challenges. In this study, a novel bifunctional electrocatalyst, Irn-CoMoPOx, was achieved via incorporating low-loading Ir single atoms and clusters with the high-valence Mo6+ modified CoPOx nanosheets. The Irn-CoMoPOx catalyst demonstrates remarkable low overpotentials of 222 mV and 36 mV for the OER and HER, respectively, in delivering a current density of 10 mA cm-2. When employed as both the anode and cathode catalyst in overall water splitting, the Irn-CoMoPOx∥Irn-CoMoPOx configuration exhibits a superior cell voltage of 1.53 V, outperforming the benchmark Pt/C∥IrO2 electrolytic cell (1.60 V) for achieving the current density of 10 mA cm-2. Benefiting from the high-valence of Mo species, the metal-support interaction of Irn-CoMoPOx was greatly strengthened, resulting in an order of magnitude increase in the mass activity of Ir for the HER. The high valence of non-noble metals plays a crucial role in tuning the local electronic configurations and optimizing the adsorption energies of the intermediates, which synergistically improves the overall performance of Ir in water splitting. The study provides valuable insights for future research in the utilization of Ir-based bifunctional catalysts for overall water electrocatalysis applications.
Keywords: Ir-based bifunctional electrocatalysts; hydrogen evolution reaction; oxygen evolution reaction; single atoms and clusters; water splitting.