Electrostatic and Electronic Effects on Doped Nickel Oxide Nanofilms for Water Oxidation

An ideal water-splitting electrocatalyst is inexpensive, abundant, highly active, stable, selective, and durable. The anodic oxygen evolution reaction (OER) is the main bottleneck for H₂ production with a complex and not fully resolved mechanism, slow kinetics, and high overpotential. Nickel oxide-based catalysts (NiO) are highly active and cheaper than precious metal catalysts. However, rigorous catalyst tests and DFT calculations are still needed to rationally optimize NiO catalysts. In this work, we combine plasma-enhanced atomic layer deposition (PE-ALD) and density functional theory (DFT) to address the role of dopants in promoting NiO OER activity. Ultrathin films of NiO doped with Zn²⁺, Al³⁺, and Sn⁴⁺ presented improved intrinsic activity, stability, and durability for the OER. The results show a low to high catalytic performance of ZnNiO < NiO < AlNiO < SnNiO, which we attribute to an increase in the concentration of valence band (VB) holes combined with conduction band (CB) electron conductivity, characterized by electrochemical impedance spectroscopy (EIS). The influence of doping on the electronic structure and catalytic activity was investigated using advanced characterization techniques and density functional theory (DFT) calculations (PEB0/pob-TZVP). DFT complements the experimental results, showing that the dopant charge states and orbital hybridization enhance the OER by improving the charge carrier concentration and mobility, thus allowing optimal binding energies and charge dynamics and delocalization. Our findings demonstrate the potential of PE-ALD-doped nanofilms NiO and DFT to rationally design and develop catalysts for sustainable energy applications.