Manipulating electron redistribution between iridium and CoMoC bridging with a carbon layer leads to a significantly enhanced overall water splitting performance at industrial-level current density.

Nowadays, alkaline water electrocatalysis is regarded as an economical and highly effective approach for large-scale hydrogen production. Highly active electrocatalysts functioning under large current density are urgently required for practical industrial applications. In this work, we present a meticulously designed methodology to anchor Ir nanoparticles on CoMoC nanofibers (CoMoC-Ir NFs) bridging with nitrogen-doped carbon as efficient bifunctional electrocatalysts with both excellent hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity and stability in alkaline media. With a low Ir content of 5.9 wt%, CoMoC-Ir NFs require the overpotentials of only 348 and 316 mV at 1 A cm for the HER and OER, respectively, and both maintain stability for at least 500 h at ampere-level current density. Consequently, an alkaline electrolyzer based on CoMoC-Ir NFs only needs a voltage of 1.5 V to drive 10 mA cm and possesses excellent durability for 500 h at 1 A cm. Density functional theory calculations reveal that the introduction of Ir nanoparticles is pivotal for the enhanced electrocatalytic activity of CoMoC-Ir NFs. The induced interfacial electron redistribution between Ir and CoMoC bridging with nitrogen-doped carbon dramatically modulates the electron structure and activates inert atoms to generate more highly active sites for electrocatalysis. Moreover, the optimized electronic structure is more conducive to the balance of the adsorption and desorption energies of reaction intermediates, thus significantly promoting the HER, OER and overall water splitting performance.