Achieving High-Performance Electrocatalytic Water Oxidation on Ni(OH) 2 with Optimized Intermediate Binding Energy Enabled by S-Doping and CeO 2 -Interfacing.

The adsorption energy of the reaction intermediates has a crucial influence on the electrocatalytic activity. Ni-based materials possess high oxygen evolution reaction (OER) performance in alkaline, however too strong binding of *OH and high energy barrier of the rate-determining step (RDS) severely limit their OER activity. Herein, a facile strategy is shown to fabricate novel vertical nanorod-like arrays hybrid structure with the interface contact of S-doped Ni(OH) 2 and CeO 2 in situ grown on Ni foam (S-Ni(OH) 2 /CeO 2 /NF) through a one-pot route. The alcohol molecules oxidation reaction experiments and theoretical calculations demonstrate that S-doping and CeO 2 -interfacing significantly modulate the binding energies of OER intermediates toward optimal value and reduce the energy barrier of the RDS, contributing to remarkable OER activity for S-Ni(OH) 2 /CeO 2 /NF with an ultralow overpotential of 196 mV at 10 mA cm -2 and long-term durability over 150 h for the OER. This work offers an efficient doping and interfacing strategy to tune the binding energy of the OER intermediates for obtaining high-performance electrocatalysts.