Decoupling Bubble Nucleation from Catalysis to Boost Cu _<i>x</i> O/NiO Electrocatalytic Water Splitting

Efficient water splitting requires low overpotentials and mitigated bubble-induced mass transfer resistance at high current densities. However, the conflict between catalysis and bubble management intensifies at these currents, blocking mass transfer and rendering the catalytic sites inaccessible. Here, we embed Cu_<i>x</i>O nucleation promoters in NiO nanosheet arrays to minimize overpotentials in electrochemical water splitting by decoupling bubble release from catalytic activity. Electrochemical measurements confirm a drastically reduced activation and mass transfer overpotential. Operando high-speed imaging combined with deep learning quantifies accelerated O₂ bubble dynamics at the Cu_<i>x</i>O/NiO/NF interface. DFT calculations and Monte Carlo simulations show Cu_<i>x</i>O acts as both O₂ bubble nucleation sites and a catalytic promoter for water splitting. An anion exchange membrane water electrolysis cell with Cu_<i>x</i>O/NiO/NF delivers a current density of 3 A cm^-2 at 2.13 V (ambient temperature). This bubble-catalysis-decoupling methodology and mechanistic insight will enable the rational design of advanced electrocatalytic systems for high-current density operation.